Synthesis of Trimethylstannyl Arylboronate Compounds by Sandmeyer-Type Transformations and Their Applications in Chemoselective Cross-Coupling Reactions
英文原文与中文译文逐段对照 · English original with Chinese translation
Di Qiu, ${}^{ \dagger }$ Shuai Wang, ${}^{ \dagger }$ Shengbo Tang, ${}^{ \dagger }$ He Meng, ${}^{ \dagger }$ Liang Jin, ${}^{ \dagger }$ Fanyang Mo, ${}^{ \dagger }$ Yan Zhang, ${}^{ \dagger }$ and Jianbo Wang*, ${}^{\dagger , \ddagger }$
邱迪，${}^{ \dagger }$ 王帅，${}^{ \dagger }$ 汤胜波，${}^{ \dagger }$ 何萌，${}^{ \dagger }$ 金亮，${}^{ \dagger }$ 莫凡洋，${}^{ \dagger }$ 张岩，${}^{ \dagger }$ 及王建波*，${}^{\dagger , \ddagger }$
${}^{ \dagger }$ Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China
${}^{ \dagger }$ 北京分子科学国家实验室(BNLMS)，教育部生物有机化学与分子工程重点实验室，北京大学化学与分子工程学院，北京 100871，中国
${}^{ \ddagger }$ State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
${}^{ \ddagger }$ 中国科学院有机金属化学国家重点实验室，上海 200032，中国
S Supporting Information
S 支持信息
ABSTRACT: A synthetic method based on Sandmeyer-type reactions to access both tin- and boron-substituted arenes from nitroaniline derivatives is described. This transformation can be applied to the synthesis of a series of functionalized trimethylstannyl arylboronates. In addition, the chemoselective reaction of the Stille and Suzuki-Miyaura cross-coupling reactions is explored, and a series of $m$ - and $p$ -terphenyl derivatives have been synthesized by conducting consecutive one-pot Stille and Suzuki-Miyaura cross-coupling reactions.
摘要:描述了一种基于桑德迈尔型反应从硝基苯胺衍生物制备锡和硼取代芳烃的合成方法。该转化可应用于一系列功能化三甲基锡基芳基硼酸酯的合成。此外，还探索了施蒂勒反应和铃木 - 宫浦交叉偶联反应的化学选择性反应，并通过连续一锅法施蒂勒反应和铃木 - 宫浦交叉偶联反应合成了一系列 $m$ - 和 $p$ - 三联苯衍生物。
I INTRODUCTION
I 引言
The transition-metal-catalyzed cross-coupling reaction has been well-established as a powerful method for the formation of $\mathrm{C} -$ C bonds. ${}^{1}$ In particular, the Stille ${}^{2}$ and Suzuki-Miyaura ${}^{3}$ cross-coupling reactions have shown widespread applications in natural product synthesis, medicinal chemistry, organic materials, and other fields. To further explore the synthetic applications of transition-metal-catalyzed coupling reactions, the iterative cross-coupling reactions have attracted attention in recent years. This strategy, which explores the different reactivities of electrophilic and nucleophilic cross-coupling partners, allows for multiple C-C bond formations in a “controlled” manner to rapidly construct functional molecules with complex structures. ${}^{4}$
过渡金属催化的交叉偶联反应已被公认为是形成$\mathrm{C} -$C键的有力方法。${}^{1}$特别是，Stille${}^{2}$和Suzuki-Miyaura${}^{3}$交叉偶联反应在天然产物合成、药物化学、有机材料及其他领域已得到广泛应用。为进一步探索过渡金属催化偶联反应的合成应用，迭代交叉偶联反应近年来受到关注。该策略利用亲电和亲核交叉偶联伙伴的不同反应活性，能够以“可控”方式多次形成C-C键，从而快速构建结构复杂的功能分子。${}^{4}$
In general, the relative reactivity of different electrophilic coupling partners decreases in the order of I > OTf > Br ≫ Cl. ${}^{3\mathrm{c}}$ Based on this order, some electrophile-selective cross-coupling reactions have been reported. ${}^{5}$ In contrast, nucleophile-selective cross-coupling reactions have rarely been developed, presumably due to the difficulty in accessimg the substrates containing multiple nucleophilic coupling sites. ${}^{6}$ To date, there are only a few examples in which the synthesis of aryl compounds containing both tin and boron substituents in the same aromatic ring and their applications in stepwise chemoselective cross-coupling reactions have been reported. ${}^{6a}$ Consequently, the development of a practical synthetic method for stannyl arylboronates is the linchpin in this area.
一般来说，不同亲电偶联伙伴的相对反应活性按I > OTf > Br ≫ Cl的顺序降低。${}^{3\mathrm{c}}$基于此顺序，已报道了一些亲电试剂选择性交叉偶联反应。${}^{5}$相比之下，亲核试剂选择性交叉偶联反应很少被开发，可能是由于难以获得含有多个亲核偶联位点的底物。${}^{6}$迄今为止，仅有少数例子报道了在同一芳环中同时含有锡和硼取代基的芳基化合物的合成及其在逐步化学选择性交叉偶联反应中的应用。${}^{6a}$因此，开发一种实用的三甲基锡基芳基硼酸酯合成方法是该领域的关键。
The reported synthetic methods for both tin- and boron-substituted benzene and thiophene start from bromophenyl boronic acid ${}^{6\mathrm{a}}$ and bis(stannyl) thiophene, ${}^{6\mathrm{\;b},\mathrm{\;d}}$ respectively (Scheme 1, paths a and b). Both of these routes involve lithiation under cryogenic reaction conditions, followed by nucleophilic attack to tin or boron electrophiles. The drawbacks of these two methods are (1) the use of much valued starting materials, (2) the need for protection and deprotection steps in some cases, and (3) the use of lithium reagents, which results in low functional-group compatibility. Inspired by our recently reported metal-free approaches toward arylboronate and arylstannane syntheses, ${}^{7,8}$ we envisaged that stannyl arylboro-nates could be accessed by simple combination of two Sandmeyer-type transformations ${}^{9,{10}}$ by starting from diamino arenes or their surrogates. In view of the operational simplicity, we chose nitro-substituted anilines as the starting materials, which are in many cases inexpensive and commercially available. Our previous study has shown that the conversion of the amino group of nitro-substituted aniline into a boronate group is highly efficient. ${}^{7}$ Moreover, the reaction conditions for nitro reduction are expected compatible with boronate substituents. Thus, a new synthetic scenario has been conceived as shown in Scheme 1(c).
已报道的用于合成含锡和硼取代的苯和噻吩的方法分别从溴苯基硼酸${}^{6\mathrm{a}}$和双(锡基)噻吩${}^{6\mathrm{\;b},\mathrm{\;d}}$开始(方案1，路径a和b)。这两条路线都涉及在低温反应条件下进行锂化，然后对锡或硼亲电试剂进行亲核进攻。这两种方法的缺点是:(1)使用昂贵的起始原料；(2)在某些情况下需要保护和脱保护步骤；(3)使用锂试剂，导致官能团兼容性低。受我们最近报道的无金属合成芳基硼酸酯和芳基锡烷方法的启发，${}^{7,8}$我们设想通过从二氨基芳烃或其替代物开始，简单组合两个桑德迈尔型转化${}^{9,{10}}$来获得三甲基锡基芳基硼酸酯。鉴于操作简便，我们选择硝基取代的苯胺作为起始原料，在许多情况下它们价格低廉且可商购。我们之前的研究表明，将硝基取代苯胺的氨基转化为硼酸酯基团的效率很高。${}^{7}$此外，硝基还原的反应条件预计与硼酸酯取代基兼容。因此，如图1(c)所示，构思了一种新的合成方案。
I RESULTS AND DISCUSSION
I 结果与讨论
We started our investigation by first converting a series of nitro anilines into nitro arylboronates by our previously reported methodology. ${}^{7\mathrm{a},\mathrm{b}}$ As shown in Scheme 2, the metal-free borylation proceeded smoothly at room temperature in moderate to good yields (49-86%) on gram scale. A broad range of functional groups, including halogen and cyano groups, which are not compatible with the lithium reagent in previously reported lithiation-based methods, ${}^{6}$ are tolerated in this transformation. In addition, it is noteworthy to point out that the yield of some ortho-substituted anilines was improved as compared to our previous studies, ${}^{7\mathrm{a},\mathrm{b}}$ most likely due to the nitro group substituted on the para position (2c-g).
我们首先采用之前报道的方法将一系列硝基苯胺转化为硝基芳基硼酸酯，以此展开研究。${}^{7\mathrm{a},\mathrm{b}}$ 如图2所示，无金属硼化反应在室温下顺利进行，克级规模的产率适中至良好(49 - 86%)。该转化反应能够耐受多种官能团，包括在之前基于锂试剂的锂化方法中与锂试剂不兼容的卤素和氰基。${}^{6}$ 此外，值得指出的是，与我们之前的研究相比，一些邻位取代苯胺的产率有所提高，${}^{7\mathrm{a},\mathrm{b}}$ 这很可能是由于对位上的硝基取代(2c - g)。
Received: November 25, 2013
收到日期:2013年11月25日
Published: February 13, 2014
发表日期:2014年2月13日
Scheme 1. Synthesis of Tin- and Boron-Substituted Arenes
方案1. 锡和硼取代芳烃的合成
Scheme 2. Metal-Free Borylation of Nitro Anilines ${}^{a}$
方案2. 硝基苯胺的无金属硼化反应 ${}^{a}$
${}^{a}$ Reaction conditions: arylamine (20 mmol), $t$ -BuONO (30 mmol,1.5 equiv), (Bpin) ${}_{2}$ (20 mmol,1 equiv), BPO (0.4 mmol,2 mol %), $\mathrm{{MeCN}}\left( {{50}\mathrm{\;{mL}}}\right)$ , room temperature, $4\mathrm{\;h}.{}^{b}$ Isolated yield.
${}^{a}$ 反应条件:芳胺(20 mmol)，$t$ -叔丁基亚硝酸酯(30 mmol，1.5当量)，(Bpin) ${}_{2}$ (20 mmol，1当量)，过氧化苯甲酰(0.4 mmol，2 mol%)，$\mathrm{{MeCN}}\left( {{50}\mathrm{\;{mL}}}\right)$ ，室温，$4\mathrm{\;h}.{}^{b}$ 分离产率。
The purified nitro arylboronates $2\mathbf{a} - \mathbf{k}$ were then converted to the amino-substituted arylboronates by Pd-catalyzed hydrogenation (Scheme 3). In general, the amino-substituted arylboronates were isolated in good to excellent yields. Low yields observed for bromo- or chloro-substituted substrates (3d, f, i) in the hydrogenation reaction could be improved by changing the solvent to DCE (1,2-dichloroethane). Under the hydrogenation conditions, the reduction of the cyano group was observed, which resulted in a lower yield of product 3g.
然后通过钯催化氢化反应将纯化后的硝基芳基硼酸酯 $2\mathbf{a} - \mathbf{k}$ 转化为氨基取代的芳基硼酸酯(方案3)。一般来说，氨基取代的芳基硼酸酯的分离产率良好至优异。氢化反应中溴代或氯代底物(3d，f，i)产率较低的情况可通过将溶剂改为1,2 -二氯乙烷(DCE)得到改善。在氢化条件下，观察到氰基被还原，这导致产物3g的产率较低。
Subsequently, typical Sandmeyer-type stannylation conditions converted the boron-substituted aniline derivatives 3a-k to the corresponding stannylation products $4\mathbf{a} - \mathbf{k}$ in moderate to good yields (Scheme 4). Compared with $p$ -boron-substituted anilines, the meta-substituted substrate afforded the stannyla-tion product in slightly lower yield (4b). The low yield of 4i might be due to the steric bulkiness of the $o$ -chloro substituent. Similarly, the substrate with methyl in the ortho position (3j) only gave a trace of stannylation product. In the case of $3\mathrm{k}$ , the hydrodeamination occurred and the expected product was not produced. Thus, in these cases, instead of the stannylation we have carried out borylation, and the corresponding diboronates were obtained in moderate yields (4i’, j, k).
随后，典型的桑德迈尔型锡化反应条件将硼取代的苯胺衍生物3a - k转化为相应的锡化产物 $4\mathbf{a} - \mathbf{k}$ ，产率适中至良好(方案4)。与 $p$ -硼取代苯胺相比，间位取代底物得到的锡化产物产率略低(4b)。4i产率低可能是由于 $o$ -氯取代基的空间位阻较大。同样，邻位有甲基的底物(3j)仅得到微量的锡化产物。对于 $3\mathrm{k}$ ，发生了加氢脱氨反应，未得到预期产物。因此，在这些情况下，我们没有进行锡化反应，而是进行了硼化反应，得到了产率适中的相应双硼酸酯(4i’，j，k)。
Scheme 3. Reduction of Nitro-Substituted Arylboronic Esters ${}^{a}$
方案3. 硝基取代芳基硼酸酯的还原反应 ${}^{a}$
${}^{a}$ Reaction conditions: nitro arylboronates $2\mathrm{a} - \mathrm{k}\left( {5\mathrm{{mmol}}}\right) ,\mathrm{{Pd}}/\mathrm{C}$ (0.25 mmol, 5 mol %), ${\mathrm{H}}_{2}$ (1 atm, balloon), MeOH (25 mL), room temperature,4 h. ${}^{b}$ Isolated yield. ${}^{c}$ 1,2-Dichloroethane used as the solvent $\left( {{25}\mathrm{\;{mL}}}\right)$ .
${}^{a}$ 反应条件:硝基芳基硼酸酯 $2\mathrm{a} - \mathrm{k}\left( {5\mathrm{{mmol}}}\right) ,\mathrm{{Pd}}/\mathrm{C}$ (0.25 mmol，5 mol%)，${\mathrm{H}}_{2}$ (1个大气压，气球)，甲醇(25 mL)，室温，4小时。${}^{b}$ 分离产率。${}^{c}$ 以1,2 -二氯乙烷为溶剂 $\left( {{25}\mathrm{\;{mL}}}\right)$ 。
To demonstrate the practical application of this synthetic method, we have conducted gram-scale experiments, with substrates 3a and 3b as examples. As shown in eqs 1 and 2, the
为了证明这种合成方法的实际应用，我们以底物3a和3b为例进行了克级规模的实验。如式1和式2所示，
Scheme 4. Stannylation and Borylation of Boron-Substituted Aniline Derivatives $3\mathrm{a} - {\mathrm{k}}^{a, b}$
方案4. 硼取代苯胺衍生物的锡化和硼化反应 $3\mathrm{a} - {\mathrm{k}}^{a, b}$
${}^{a}$ For stannylation reaction conditions: boron-substituted arylamine (0.3 mmol), t-BuONO (0.36 mmol, 1.2 equiv), (SnMe ${}_{3}$ ), (0.33 mmol, 1.1 equiv), TsOH (0.36 mmol, 1.2 equiv), DCE (1.5 mL), 0°C, 4 h. ${}^{b}$ For borylation reaction conditions: boron-substituted arylamine (0.3 mmol), t-BuONO (0.45 mmol, 1.5 equiv), (Bpin) (0.33 mmol, 1.1 equiv), BPO (0.006 mmol, 2 mol %), MeCN (1 mL), room temperature, $4\mathrm{\;h}$ . ZIsolated yield.
${}^{a}$ 对于锡化反应条件:硼取代芳胺(0.3 mmol)，叔丁基亚硝酸酯(0.36 mmol，1.2当量)，(SnMe ${}_{3}$ )(0.33 mmol，1.1当量)，对甲苯磺酸(0.36 mmol，1.2当量)，1,2-二氯乙烷(1.5 mL)，0°C，4小时。 ${}^{b}$ 对于硼化反应条件:硼取代芳胺(0.3 mmol)，叔丁基亚硝酸酯(0.45 mmol，1.5当量)，(Bpin)(0.33 mmol，1.1当量)，二叔丁基过氧化物(0.006 mmol，2 mol%)，乙腈(1 mL)，室温，$4\mathrm{\;h}$ 。Z为分离产率。
gram-scale stannylation reactions afforded the corresponding products $4\mathbf{a}$ and $4\mathbf{b}$ in moderate yields, respectively.
克级锡化反应分别以中等产率得到相应产物$4\mathbf{a}$ 和$4\mathbf{b}$ 。
(1) (2)
With these stannyl arylboronate compounds in hand, we then turned our attention to investigate the chemoselective reactivity of 4a under Stille cross-coupling reaction conditions. By using a series of aryl bromides as electrophilic coupling partners, the corresponding biphenyl boronates were obtained in good to excellent yields (Scheme 5). This coupling reaction has good tolerance to both electron-donating (5f) and electron-withdrawing groups (5a-e) on the aromatic rings of aryl bromides. Furthermore, heteroaromatic halides were also subjected to this reaction with good results (5i, j).
有了这些三甲基锡基芳基硼酸酯化合物后，我们接着将注意力转向研究4a在Stille交叉偶联反应条件下的化学选择性反应活性。通过使用一系列芳基溴化物作为亲电偶联伙伴，以良好至优异的产率得到了相应的联苯硼酸酯(方案5)。该偶联反应对芳基溴化物芳环上的供电子基团(5f)和吸电子基团(5a - e)均具有良好的耐受性。此外，杂芳基卤化物也能顺利进行该反应(5i，j)。
Scheme 5. Stille Cross-Coupling Reaction with $4{\mathrm{a}}^{a}$
方案5. 与$4{\mathrm{a}}^{a}$ 的Stille交叉偶联反应
${}^{a}$ Reaction condition: 4a (0.5 mmol), ArBr (0.5 mmol,1.0 equiv), $\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right)$ , toluene $\left( {3\mathrm{\;{mL}}}\right) ,{110}{}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$ . ${}^{b}$ Isolated yield. ${}^{c}$ Reaction condition: 4a ( ${0.5}\mathrm{{mmol}}$ ), $\mathrm{{ArBr}}$ ( ${0.5}\mathrm{{mmol}}$ , 1.0 equiv), $\mathrm{{Pd}}{\left( \mathrm{{OAc}}\right) }_{2}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right) ,\mathrm{P}{\left( o\text{ -tol }\right) }_{3}({0.1}\mathrm{{mmol}},{20}$ mol %), toluene $\left( {3\mathrm{\;{mL}}}\right) ,{110}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$ .
${}^{a}$ 反应条件:4a(0.5 mmol)，芳基溴(0.5 mmol，1.0当量)，$\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right)$ ，甲苯$\left( {3\mathrm{\;{mL}}}\right) ,{110}{}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$ 。 ${}^{b}$ 分离产率。 ${}^{c}$ 反应条件:4a(${0.5}\mathrm{{mmol}}$ )，$\mathrm{{ArBr}}$ (${0.5}\mathrm{{mmol}}$ ，1.0当量)，$\mathrm{{Pd}}{\left( \mathrm{{OAc}}\right) }_{2}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right) ,\mathrm{P}{\left( o\text{ -tol }\right) }_{3}({0.1}\mathrm{{mmol}},{20}$ mol%)，甲苯$\left( {3\mathrm{\;{mL}}}\right) ,{110}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$ 。
Similarly, we have taken $m$ -tin-substituted arylboronate 4b as the substrate and performed the chemoselective Stille cross-coupling reaction with aryl bromides (Scheme 6). In all cases of aryl (6a-c), thiophenic (6d), and pyridine halides (6e), the coupling reaction afforded the corresponding biphenyl products in high yields, with the retention of the boron group.
同样，我们以$m$ -锡取代的芳基硼酸酯4b为底物，与芳基溴化物进行化学选择性Stille交叉偶联反应(方案6)。在芳基(6a - c)、噻吩基(6d)和吡啶卤化物(6e)的所有情况下，偶联反应均以高产率得到相应的联苯产物，且硼基团得以保留。
Finally, to further demonstrate the usefulness of stannyl arylboronates, we carried out consecutive one-pot cross-coupling reactions to synthesize $m$ -terphenyl and $p$ -terphenyl compounds by using 4a and 4b as the coupling partners (Scheme 7). ${}^{7c}$ Thus, the Stille cross-coupling was first performed with $\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}$ catalyst and ArBr. Upon completion of the Stille coupling, Suzuki-Miyaura coupling was performed with ${\mathrm{{Ar}}}^{\prime }\mathrm{{Br}}$ and the same $\mathrm{{Pd}}\left( 0\right)$ catalyst, without purification of the intermediates. This one-pot coupling reaction afforded $m$ - terphenyl (7a-e) and p-terphenyl derivatives (7f-j) in moderate to good yields (Scheme 7).
最后，为了进一步证明甲锡烷基芳基硼酸酯的实用性，我们以4a和4b作为偶联伙伴，进行了连续的一锅法交叉偶联反应，以合成$m$-三联苯和$p$-三联苯化合物(方案7)。${}^{7c}$因此，首先用$\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}$催化剂和ArBr进行Stille交叉偶联。Stille偶联完成后，用${\mathrm{{Ar}}}^{\prime }\mathrm{{Br}}$和相同的$\mathrm{{Pd}}\left( 0\right)$催化剂进行Suzuki-Miyaura偶联，无需纯化中间体。该一锅法偶联反应以中等至良好的产率得到了$m$-三联苯(7a-e)和对三联苯衍生物(7f-j)(方案7)。
CONCLUSION
结论
In summary, we have developed a synthetic method for arene derivatives bearing both tin and boron substituents by a two sequential Sandmeyer-type transformations. This approach is under transition-metal-free conditions and affords highly functionalized building blocks for cross-coupling reactions in three steps from commercially available starting materials. These stannyl arylboronates can be subjected to chemoselective Stille coupling reactions with good to excellent yields. As shown by the one-pot synthesis of $p$ -terphenyl and $m$ -terphenyl derivatives bearing various functional groups, the stannyl arylboronates are highly useful in organic synthesis.
总之，我们通过连续两步的桑德迈尔型转化反应，开发了一种合成同时含有锡和硼取代基的芳烃衍生物的方法。该方法无需过渡金属，从市售原料出发，通过三步反应即可得到用于交叉偶联反应的高官能化结构单元。这些三甲基锡基芳基硼酸酯能够进行化学选择性的施蒂勒偶联反应，产率良好至优异。如一锅法合成带有各种官能团的$p$ -三联苯和$m$ -三联苯衍生物所示，三甲基锡基芳基硼酸酯在有机合成中非常有用。
Scheme 6. Stille Cross-Coupling Reaction with $4{\mathrm{\;b}}^{a}$
方案6. 与$4{\mathrm{\;b}}^{a}$的施蒂勒交叉偶联反应
${}^{a}$ Reaction conditions: 4b (0.5 mmol), ArBr (0.5 mmol,1.0 equiv), $\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right)$ , toluene $\left( {3\mathrm{\;{mL}}}\right) ,{110}{}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$ . ${}^{b}$ Isolated yield. ${}^{c}$ Reaction conditions: 4a (0.5 mmol), ArBr (0.5 mmol, 1.0 equiv), $\mathrm{{Pd}}{\left( \mathrm{{OAc}}\right) }_{2}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right) ,\mathrm{P}{\left( o - \mathrm{{tol}}\right) }_{3}({0.1}\mathrm{{mmol}},{20}$ mol %), toluene (3 mL), 110 °C, 12 h.
${}^{a}$反应条件:4b(0.5 mmol)，ArBr(0.5 mmol，1.0当量)，$\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right)$，甲苯$\left( {3\mathrm{\;{mL}}}\right) ,{110}{}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$。${}^{b}$分离产率。${}^{c}$反应条件:4a(0.5 mmol)，ArBr(0.5 mmol，1.0当量)，$\mathrm{{Pd}}{\left( \mathrm{{OAc}}\right) }_{2}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right) ,\mathrm{P}{\left( o - \mathrm{{tol}}\right) }_{3}({0.1}\mathrm{{mmol}},{20}$摩尔%，甲苯(3 mL)，110°C，12小时。
EXPERIMENTAL SECTION
实验部分
General Methods. The solvents were all distilled prior to use. MeCN, DCE, and toluene were distilled from calcium hydride. For flash column chromatography, 200-300 mesh silica gels were used. Chemical shifts for ${}^{1}\mathrm{H}$ NMR (400 MHz) and ${}^{13}\mathrm{C}$ NMR (100 MHz) spectra are reported relative to the chemical shift of tetramethylsilane (TMS). IR spectra are reported in wavenumbers, ${\mathrm{{cm}}}^{-1}$ . For HRMS measurements, the mass analyzer is FT-ICR.
一般方法。所用溶剂在使用前均经过蒸馏。乙腈、1,2 - 二氯乙烷和甲苯用氢化钙蒸馏。柱色谱使用200 - 300目的硅胶。${}^{1}\mathrm{H}$ NMR(400 MHz)和${}^{13}\mathrm{C}$ NMR(100 MHz)谱的化学位移相对于四甲基硅烷(TMS)的化学位移报告。红外光谱以波数${\mathrm{{cm}}}^{-1}$报告。高分辨质谱测量使用傅里叶变换离子回旋共振质谱仪。
Typical Procedure for the Borylation Reactions. 4-Nitroaniline (1a, 2.76 g, 20 mmol), (Bpin) ${}_{2}\left( {{20}\mathrm{{mmol}},{5.08}\mathrm{\;g}}\right)$ , and BPO (0.4 mmol, 97 mg) were weighed in a 250 mL round-bottom flask. MeCN $\left( {{60}\mathrm{\;{mL}}}\right)$ and $t$ -BuONO $\left( {{30}\mathrm{\;{mmol}},{3.09}\mathrm{\;g}}\right)$ were then added in succession. The resulting clear reaction mixture was allowed to stir for $4\mathrm{\;h}$ at room temperature (nitrogen gas evolution completed within 1 h). The mixture was then concentrated under reduced pressure, and the crude residue was purified by silica gel flash column chromatography (petroleum ether/EtOAc = 500:1) and afforded 4,4,5,5-tetramethyl-2-(4-nitrophenyl)-1,3,2-dioxaborolane (2a) (3.88 g,78%) as a yellow solid: ${}^{7\mathrm{a}}\mathrm{{mp}} = {109} - {110}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.19 (d, $J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.96 (d, $J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}$ ),1.37 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.8,135.6,122.3,84.6,24.8; IR (film) 2975,1788,1518,1363,1349,1147,860,851,697 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 249 (M ${}^{ + }$ ,18),234 (100),163 (85),150 (43), 149 (22), 104 (22), 85 (23), 58 (46), 43 (46), 42 (59).
硼化反应的典型步骤。在250 mL圆底烧瓶中称取4 - 硝基苯胺(1a，2.76 g，20 mmol)、(Bpin)${}_{2}\left( {{20}\mathrm{{mmol}},{5.08}\mathrm{\;g}}\right)$和过氧化苯甲酰(0.4 mmol，97 mg)。然后依次加入乙腈$\left( {{60}\mathrm{\;{mL}}}\right)$和$t$ - 丁基亚硝酸酯$\left( {{30}\mathrm{\;{mmol}},{3.09}\mathrm{\;g}}\right)$。所得澄清反应混合物在室温下搅拌$4\mathrm{\;h}$(1小时内氮气释放完毕)。然后减压浓缩混合物，粗残余物通过硅胶柱色谱(石油醚/乙酸乙酯 = 500:1)纯化，得到4,4,5,5 - 四甲基 - 2 - (4 - 硝基苯基)-1,3,2 - 二氧硼戊环(2a)(3.88 g，78%)，为黄色固体:${}^{7\mathrm{a}}\mathrm{{mp}} = {109} - {110}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR(400 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 8.19(d，$J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}$)，7.96(d，$J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}$)，1.37(s，12H)；${}^{13}\mathrm{C}$ NMR(100 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 149.8，135.6，122.3，84.6，24.8；红外(薄膜)2975，1788，1518，1363，1349，1147，860，851，697${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)249(M${}^{ + }$，18)，234(100)，163(85)，150(43)，149(22)，104(22)，85(23)，58(46)，43(46)，42(59)。
4,4,5,5-Tetramethyl-2-(3-nitrophenyl)-1,3,2-dioxaborolane (2b). ${}^{a}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 2b (2.49 g, 50%): yellow solid; mp = 74-76 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ 8.64 $\left( {\mathrm{d}, J = {1.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.31} - {8.28}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{8.10}(\mathrm{\;d}, J = {7.6} \; \mathrm{{Hz}},1\mathrm{H}),{7.56} - {7.52}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},}\right) \; {\mathrm{{CDCl}}}_{3}$ ) $\delta$ 147.8, 140.6, 129.4, 128.7, 125.8, 84.6, 24.9; IR (film) 2980, 1530,1362,1344,1145,1123,852,694 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 249 (M ${}^{ + }$ , 8), 234 (100), 163 (35), 150 (85), 147 (46), 121 (75), 85 (30), 57 (26).
4,4,5,5-四甲基-2-(3-硝基苯基)-1,3,2-二氧硼戊环(2b)。${}^{a}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到2b(2.49 g，产率50%):黄色固体；熔点=74 - 76°C；${}^{1}\mathrm{H}$核磁共振氢谱(400 MHz，${\mathrm{{CDCl}}}_{3})\delta$ 8.64 $\left( {\mathrm{d}, J = {1.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.31} - {8.28}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{8.10}(\mathrm{\;d}, J = {7.6} \; \mathrm{{Hz}},1\mathrm{H}),{7.56} - {7.52}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},}\right) \; {\mathrm{{CDCl}}}_{3}$ ) $\delta$ 147.8, 140.6, 129.4, 128.7, 125.8, 84.6, 24.9；红外光谱(薄膜)2980, 1530,1362,1344,1145,1123,852,694 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$(m/z$ ，相对强度)249(M ${}^{ + }$ , 8), 234(100), 163(35), 150(85), 147(46), 121(75), 85(30), 57(26)。
4,4,5,5-Tetramethyl-2-(2-methyl-4-nitrophenyl)-1,3,2-dioxaboro-lane (2c). ${}^{11}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1) afforded 2c (4.52 g, 86%) as a yellow solid: mp = 56-57°C; ${}^{1}$ H NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.99 (s,1H),7.97 (d, $J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}),{7.89}$ (d, $J = {8.2} \; \mathrm{{Hz}},1\mathrm{H}),{2.63}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.2, 146.5, 136.6, 123.8, 119.2, 84.1, 24.8, 22.0; IR (film) 2980, ${1520},{1338},{1288},{1143},{1064},{814},{721}{\mathrm{\;{cm}}}^{-1}$ . EI-MS $(m/z$ , relative intensity) 263 (M ${}^{ + }$ , 4), 248 (100), 206 (79), 177 (13), 164 (69), 117 (22), 59 (23).
4,4,5,5-四甲基-2-(2-甲基-4-硝基苯基)-1,3,2-二氧硼戊环(2c)。${}^{11}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1)得到2c(4.52 g，产率86%)，为黄色固体:熔点=56 - 57°C；${}^{1}$核磁共振氢谱(400 MHz，CDCl ${}_{3}$ ) $\delta$ 7.99(s,1H),7.97(d, $J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}),{7.89}$ (d, $J = {8.2} \; \mathrm{{Hz}},1\mathrm{H}),{2.63}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振碳谱(100 MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.2, 146.5, 136.6, 123.8, 119.2, 84.1, 24.8, 22.0；红外光谱(薄膜)2980, ${1520},{1338},{1288},{1143},{1064},{814},{721}{\mathrm{\;{cm}}}^{-1}$ 。电子轰击质谱$(m/z$ ，相对强度)263(M ${}^{ + }$ , 4), 248(100), 206(79), 177(13), 164(69), 117(22), 59(23)。
Scheme 7. Consecutive One-Pot Stille and Suzuki-Miyaura Cross-Coupling Reactions ${}^{a}$
方案7. 连续一锅法施蒂勒和铃木-宫浦交叉偶联反应 ${}^{a}$
${}^{a}$ Reaction conditions for the first step: 4a or 4b (0.5 mmol), ArBr (0.5 mmol, 1.0 equiv), Pd(PPh ${}_{3}{)}_{4}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right)$ , toluene (3 mL), ${110}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$ ; second step: Ar’Br (0.525 mmol,1.05 equiv), ${\mathrm{K}}_{2}{\mathrm{{CO}}}_{3}$ (1.0 mmol,2 equiv), $\mathrm{{EtOH}}/{\mathrm{H}}_{2}\mathrm{O}\left( {1\mathrm{\;{mL}}/1\mathrm{\;{mL}}}\right) ,{90}^{ \circ }\mathrm{C},{12}\mathrm{\;h}.{}^{b}$ Isolated yield.
${}^{a}$ 第一步反应条件:4a或4b(0.5 mmol)，ArBr(0.5 mmol，1.0当量)，Pd(PPh ${}_{3}{)}_{4}\left( {{0.025}\mathrm{{mmol}},5\mathrm{\;{mol}}\% }\right)$ ，甲苯(3 mL)，${110}^{ \circ }\mathrm{C},{12}\mathrm{\;h}$ ；第二步:Ar’Br(0.525 mmol，1.05当量)，${\mathrm{K}}_{2}{\mathrm{{CO}}}_{3}$ (1.0 mmol，2当量)，$\mathrm{{EtOH}}/{\mathrm{H}}_{2}\mathrm{O}\left( {1\mathrm{\;{mL}}/1\mathrm{\;{mL}}}\right) ,{90}^{ \circ }\mathrm{C},{12}\mathrm{\;h}.{}^{b}$ 分离产率。
2-(2-Chloro-4-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-lane (2d). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1) afforded 2d (2.80 g, 49%) as a yellow solid:mp =66-67°C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 8.20 (d, $J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}$ ), 8.06 (dd, $J = {2.0},{8.2}\mathrm{\;{Hz}}$ , 1H), 7.85 (d, J = 8.2 Hz, 1H), 1.39 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 149.7, 140.5, 137.0, 124.1, 120.4, 84.9, 24.8; IR (film) 2981, 1525,1384,1341,1143,1037,890,732 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${283}\left( {{\mathrm{M}}^{ + },2}\right) ,{268}\left( {29}\right) ,{248}\left( {100}\right) ,{206}\left( {42}\right) ,{184}\left( {26}\right) ,{85}$ (15),59 (14); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{16}{\mathrm{\;B}}^{35}{\mathrm{{ClNO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 284.0858, found 284.0859.
2-(2-氯-4-硝基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(2d)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1)得到黄色固体2d(2.80 g，49%):熔点=66 - 67°C；${}^{1}\mathrm{H}$核磁共振(400兆赫，CDCl${}_{3}$)$\delta$8.20(双峰，$J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}$)，8.06(双重峰，$J = {2.0},{8.2}\mathrm{\;{Hz}}$，1H)，7.85(双峰，J = 8.2赫兹，1H)，1.39(单峰，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl${}_{3}$)δ149.7，140.5，137.0，124.1，1,20.4，84.9，24.8；红外光谱(薄膜)2981，1525，1384，1341，1143，1037，890，732${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)${283}\left( {{\mathrm{M}}^{ + },2}\right) ,{268}\left( {29}\right) ,{248}\left( {100}\right) ,{206}\left( {42}\right) ,{184}\left( {26}\right) ,{85}$(15)，59(14)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{16}{\mathrm{\;B}}^{35}{\mathrm{{ClNO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$284.0858，实测值为284.0859。
2-(2-Fluoro-4-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-lane (2e). ${}^{12}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 2e (2.72 g, 51%) as a yellow solid: mp = ${63} - {64}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 8.00 (dd, $J = {2.0},{8.2}\mathrm{\;{Hz}},1\mathrm{H}$ ), 7.92 (dd, $J = {5.7},{8.2} \; \mathrm{{Hz}},1\mathrm{H}),{7.88}\left( {\mathrm{{dd}}, J = {2.0},{8.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.38}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}({100}$ MHz, CDCl ${}_{3}$ ) $\delta$ 166.6 $\left( {\mathrm{d}, J = {255.5}\mathrm{\;{Hz}}}\right) ,{150.9}\left( {\mathrm{\;d}, J = {9.0}\mathrm{\;{Hz}}}\right) ,{137.7} \; \left( {\mathrm{d}, J = {8.7}\mathrm{\;{Hz}}}\right) ,{118.3}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ,{110.9}\left( {\mathrm{\;d}, J = {29.4}\mathrm{\;{Hz}}}\right) ,{84.7}$ , 24.8; IR (film) 1726, 1529, 1416, 1346, 1143, 817, 733 cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{267}\left( {{\mathrm{M}}^{ + },8}\right) ,{252}\left( {100}\right) ,{208}\left( {25}\right) ,{205}\left( {19}\right) }\right)$ , 183 (15), 168 (17), 121 (17), 85 (18), 59 (21).
2-(2-氟-4-硝基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(2e)。${}^{12}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到黄色固体2e(2.72 g，51%):熔点=${63} - {64}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振(400 MHz，CDCl ${}_{3}$ ) $\delta$ 8.00(双重峰，$J = {2.0},{8.2}\mathrm{\;{Hz}},1\mathrm{H}$ )，7.92(双重峰，$J = {5.7},{8.2} \; \mathrm{{Hz}},1\mathrm{H}),{7.88}\left( {\mathrm{{dd}}, J = {2.0},{8.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.38}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}({100}$ MHz，CDCl ${}_{3}$ ) $\delta$ 166.6 $\left( {\mathrm{d}, J = {255.5}\mathrm{\;{Hz}}}\right) ,{150.9}\left( {\mathrm{\;d}, J = {9.0}\mathrm{\;{Hz}}}\right) ,{137.7} \; \left( {\mathrm{d}, J = {8.7}\mathrm{\;{Hz}}}\right) ,{118.3}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ,{110.9}\left( {\mathrm{\;d}, J = {29.4}\mathrm{\;{Hz}}}\right) ,{84.7}$ ，24.8；红外光谱(薄膜)1726、1529、1416、1346、1143、817、733 cm ${}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity) }{267}\left( {{\mathrm{M}}^{ + },8}\right) ,{252}\left( {100}\right) ,{208}\left( {25}\right) ,{205}\left( {19}\right) }\right)$ ，183(15)，168(17)，121(17)，85(18)，59(21)。
2-(2-Bromo-4-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-lane (2f). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1) afforded 2f (3.64 g, 55%) as a yellow solid: mp = 61-63 ${}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.39 (d, $J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}$ ),8.11 (dd, $J = {2.0},{8.2}\mathrm{\;{Hz}}$ , 1H), ${7.77}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.40}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.4,136.8,128.1,127.2,120.8,85.1,24.8; IR (film) 2981, 1524,1373,1340,1143,1124,850,731 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) 328 (M ${}^{ + }$ , 5), 312 (21), 248 (100), 228 (25), 206 (70), 160 (22),85 (22),75 (24); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{16}{\mathrm{\;B}}^{79}{\mathrm{{BrNO}}}_{4}$ [M + H] ${}^{ + }$ 328.0353, found 328.0363.
2-(2-溴-4-硝基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(2f)。按照典型程序操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1)得到黄色固体2f(3.64 g，55%):熔点61 - 63${}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$8.39(d，$J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}$)，8.11(dd，$J = {2.0},{8.2}\mathrm{\;{Hz}}$，1H)，${7.77}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.40}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$149.4，136.8，128.1，127.2，120.8，85.1，24.8；红外光谱(薄膜)2981，1524，1373，1340，1143，1124，850，731${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度)328(M${}^{ + }$，5)，312(21)，248(100)，228(25)，206(70)，160(22)，85(22)，75(24)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{16}{\mathrm{\;B}}^{79}{\mathrm{{BrNO}}}_{4}$[M + H]${}^{ + }$328.0353，实测值328.0363。
5-Nitro-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- benzonitrile (2g). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1) afforded $2\mathrm{\;g}\left( {{2.96}\mathrm{\;g},{54}\% }\right)$ as a yellow oil: ${}^{1}\mathrm{H}$ NMR $({400}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}){\delta 8.54}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.49}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.02}(\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}}$ , 1H), 1.26 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 148.2, 137.5, 127.5, 127.2, 116.5, 114.1, 83.4, 25.0; IR (film) 2980, 2232, 1533, 1352,1143,1124,1059,909,734 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 274 (M ${}^{ + }$ , 13), 259 (100), 233 (84), 216 (66), 186 (18), 175 (47), 129 (42), 102 (43), 59 (47); HRMS (ESI) calcd for ${\mathrm{C}}_{13}{\mathrm{H}}_{16}{\mathrm{{BN}}}_{2}{\mathrm{O}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{275.1200}$ , found 275.1198.
5-硝基-2-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯甲腈(2g)。按照典型程序操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1)得到$2\mathrm{\;g}\left( {{2.96}\mathrm{\;g},{54}\% }\right)$为黄色油状物:${}^{1}\mathrm{H}$核磁共振$({400}\mathrm{{MHz}}$，${\mathrm{{CDCl}}}_{3}){\delta 8.54}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.49}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.02}(\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}}$，1H)，1.26(s，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，氯仿)δ148.2，137.5，127.5，127.2，116.5，114.1，83.4，25.0；红外光谱(薄膜)2980，2232，1533，1352，1143，1124，1059，909，734${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)274(M${}^{ + }$，13)，259(100)，233(84)，216(66)，186(18)，175(47)，129(42)，102(43)，59(47)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{13}{\mathrm{H}}_{16}{\mathrm{{BN}}}_{2}{\mathrm{O}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{275.1200}$，实测值275.1198。
2-(3-Fluoro-4-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-lane (2h). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 50:1) afforded $2\mathrm{\;h}\left( {{3.26}\mathrm{\;g},{61}\% }\right)$ as a yellow solid:mp $= {85} - {87}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl, 5 Å 801 (t, J = 7.6 Hz, 1H), 7.70-7.69 (m, 1H), ${7.67}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 154.8 (d, $J = {265.4}\mathrm{\;{Hz}}$ ),139.0 (d, $J = {7.3}\mathrm{\;{Hz}}$ ),130.5 (d, $J = {4.4}\mathrm{\;{Hz}}$ ), 125.1 (d, $J = {2.9}\mathrm{\;{Hz}}$ ),124.1 (d, $J = {19.1}\mathrm{\;{Hz}}$ ),84.9,24.8; IR (film) 2981,1728,1595,1527,1410,1348,1143,837 ${\mathrm{{cm}}}^{-1}$ . EI-MS $(m/z$ , relative intensity) 267 (M ${}^{ + }$ , 8), 252 (100), 224 (12), 181 (73), 168 (13), 151 (10), 122 (16), 57 (20); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{15}{\mathrm{{BFNNaO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$ 290.0973, found 290.0973.
2-(3-氟-4-硝基苯基)-4,4,5,5-四甲基-1,3,2-二氧硼戊环(2h)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后50:1)得到$2\mathrm{\;h}\left( {{3.26}\mathrm{\;g},{61}\% }\right)$，为黄色固体:熔点$= {85} - {87}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振(400兆赫，CDCl，5埃801(t，J = 7.6赫兹，1H)，7.70 - 7.69(多重峰，1H)，${7.67}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100兆兆兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 154.8(d，$J = {265.4}\mathrm{\;{Hz}}$ )，139.0(d，$J = {7.3}\mathrm{\;{Hz}}$ )，130.5(d，$J = {4.4}\mathrm{\;{Hz}}$ )，125.1(d，$J = {2.9}\mathrm{\;{Hz}}$ )，124.1(d，$J = {19.1}\mathrm{\;{Hz}}$ )，84.9，24.8；红外光谱(薄膜)2981，1728，1595，1527，1410，13 48，1143，837 ${\mathrm{{cm}}}^{-1}$ 。电子轰击质谱$(m/z$ ，相对强度)267(M ${}^{ + }$ ，8)，252(100)，224(12)，181(73)，168(13)，151(10)，122(16)，57(20)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{15}{\mathrm{{BFNNaO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$ 290.0973，实测值为290.0973。
2-(4-Chloro-3-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-lane (2i). ${}^{7b}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1, then 100:1) afforded 2i (2.95 g,52%) as a yellow liquid: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 8.25 (d, $J = {1.3}\mathrm{\;{Hz}},1\mathrm{H}$ ),7.89 (dd, $J = {1.3},{8.0}\mathrm{\;{Hz}}$ , 1H), 7.54 (d, J = 8.0 Hz, 1H), 1.35 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 147.8, 138.9, 131.3, 131.2, 129.5, 84.8, 24.8; IR (film) 2980, 2922, 1538, 1390, 1349, 1143, 1097, 852, 732 cm ${}^{-1}$ . EI-MS (m/z, relative intensity) ${283}\left( {{\mathrm{M}}^{ + },8}\right) ,{268}\left( {85}\right) ,{223}\left( {27}\right) ,{197}\left( {36}\right) ,{181}$ (77), 155 (100), 137 (31), 85 (42), 75 (39), 58 (50).
2-(4-氯-3-硝基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(2i)。${}^{7b}$ 按照典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1，然后100:1)得到黄色液体2i(2.95 g，52%):${}^{1}\mathrm{H}$ 核磁共振氢谱(400 MHz，CDCl ${}_{3}$ ) $\delta$ δ 8.25(双峰，$J = {1.3}\mathrm{\;{Hz}},1\mathrm{H}$ )，7.89(双重峰，$J = {1.3},{8.0}\mathrm{\;{Hz}}$ ，1H)，7.54(双峰，J = 8.0 Hz，1H)，1.35(单峰，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100 MHz，CDCl3)δ 147.8，138.9，131.3，131.2，129.5，84.8，24.8；红外光谱(薄膜)2980，2922，1538，1390，1349，1143，1097，852，732 cm ${}^{-1}$ 。电子轰击质谱(质荷比，相对强度) ${283}\left( {{\mathrm{M}}^{ + },8}\right) ,{268}\left( {85}\right) ,{223}\left( {27}\right) ,{197}\left( {36}\right) ,{181}$ (77)，155(100)，137(31)，85(42)，75(39)，58(50)。
4,4,5,5-Tetramethyl-2-(4-methyl-3-nitrophenyl)-1,3,2-dioxaboro-lane (2j). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1) afforded 2j (2.89 g, 55%) as a yellow solid: mp = 71-73°C; ${}^{1}$ H NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.36 (s, 1H), 7.88 (d, J = 7.5 Hz, 1H), 7.33 (d, J = 7.5 Hz, 1H), 2.61 (s, 3H), 1.35 (s, 12H); ${}^{13}$ C NMR (100 MHz, CDCl3) $\delta$ 149.2, 138.8, 136.2, 132.2, 130.6, 84.4, 24.8, 20.5; IR (film) 2980, 1620, 1530, 1362, 1346, 1149, 1109, 853, 732 cm ${}^{-1}$ . EI-MS (m/z, relative intensity) 263 (M ${}^{ + }$ , 19), 248 (78), 203 (27), 177 (27), 164 (100), 147 (27), 135 (63), 117 (71); HRMS (ESI) calcd for ${\mathrm{C}}_{13}{\mathrm{H}}_{19}{\mathrm{{BNO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 264.1404, found 264.1398.
4,4,5,5-四甲基-2-(4-甲基-3-硝基苯基)-1,3,2-二氧硼杂环戊烷(2j)。按照典型程序操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1)得到黄色固体2j(2.89 g，55%):熔点71 - 73°C；${}^{1}$氢核磁共振谱(400兆赫，CDCl${}_{3}$)δ 8.36(单峰，1H)，7.88(双峰，J = 7.5赫兹，1H)，7.33(双峰，J = 7.5赫兹，1H)，2.61(单峰，3H)，1.35(单峰，12H)；${}^{13}$碳核磁共振谱(100兆赫，CDCl3)$\delta$ 149.2，138.8，136.2，132.2，130.6，84.4，24.8，20.5；红外光谱(薄膜)2980，1620，1530，1362，1346，1149，1109，853，732厘米${}^{-1}$。电子轰击质谱(质荷比，相对强度)263(M${}^{ + }$，19)，248(78)，203(27)，177(27)，164(100)，147(27)，135(63)，117(71)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{13}{\mathrm{H}}_{19}{\mathrm{{BNO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 264.1404，实测值为264.1398。
4,4,5,5-Tetramethyl-2-(4-nitronaphthalen-1-yl)-1,3,2-dioxaboro-lane (2k). The typical procedure was followed, and flash chromatography (silica gel, petroleum ether/EtOAc = 200:1, then 50:1) afforded 2k (4.20 g, 70%) as a orange solid: mp = 166-168 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.87 (dd, $J = {2.0},{7.5}\mathrm{\;{Hz}},1\mathrm{H}$ ),8.42 $\left( {\mathrm{{dd}}, J = {2.0},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.11}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.07}(\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}$ , 1H), 7.69-7.65 (m, 2H), 1.44 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 149.1, 138.0, 133.5, 128.9, 128.6, 127.6, 124.4, 122.8, 121.8, 84.5, 24.9; IR (film) 2981, 1765, 1518, 1346, 1329, 1141, 765 cm ${}^{-1}$ . EI-MS $\left( {m/z}\right.$ , relative intensity) 299 $\left( {{\mathrm{M}}^{ + },}\right.$ 100 $),{284}\left( {32}\right) ,{255}\left( {24}\right)$ , 213 (34), 196 (38), 153 (66), 141 (51), 83 (57); HRMS (ESI) calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{19}{\mathrm{{BNO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 300.1405, found 300.1403.
4,4,5,5-四甲基-2-(4-硝基萘-1-基)-1,3,2-二氧硼杂环戊烷(2k)。按照典型程序操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1，然后50:1)得到橙色固体2k(4.20 g，70%):熔点166 - 168°C；${}^{1}\mathrm{H}$核磁共振谱(400兆赫，CDCl${}_{3}$)δ 8.87(双重峰，$J = {2.0},{7.5}\mathrm{\;{Hz}},1\mathrm{H}$)，8.42$\left( {\mathrm{{dd}}, J = {2.0},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.11}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.07}(\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}$，1H)，7.69 - 7.65(多重峰，2H)，1.44(单峰，12H)；${}^{13}\mathrm{C}$核磁共振谱(100兆赫，CDCl${}_{3}$)δ 149.1，138.0，133.5，128.9，128.6，127.6，124.4，122.8，121.8，84.5，24.9；红外光谱(薄膜)2981，1765，1518，1346，1329，1141，765厘米${}^{-1}$。电子轰击质谱$\left( {m/z}\right.$，相对强度)299$\left( {{\mathrm{M}}^{ + },}\right.$ 100$),{284}\left( {32}\right) ,{255}\left( {24}\right)$，213(34)，196(38)，153(66)，141(51)，83(57)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{19}{\mathrm{{BNO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 300.1405，实测值为300.1403。
Typical Procedure for the Pd/C-Catalyzed Hydrogenation Reactions. 4,4,5,5-Tetramethyl-2-(4-nitrophenyl)-1,3,2-dioxaboro-lane (2a,5 mmol,1.245 g) and Pd/C (265 mg,0.25 mmol,[Pd/C] 10 wt %) were weighed in a ${100}\mathrm{\;{mL}}$ reaction tube. MeOH (25 mL) was then added in succession. The resulting reaction solution was stirred for $4\mathrm{\;h}$ at room temperature with a ${\mathrm{H}}_{2}$ balloon (1 atm). The reaction system was filtered through silica gel eluting with dichloromethane, and then the reaction mixture was concentrated under reduced pressure. The crude residue was purified by silica gel flash column chromatography (PE/EA = 15:1) to give 4-(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)aniline ${\left( 3a\right) }^{7b}$ in 98% isolated yield (1.071 g) as a pale yellow solid: $\mathrm{{mp}} = {148} - {150}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 7.62 $\left( {\mathrm{d}, J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{6.65}(\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}}$ , 2H), 3.83 (br, 2H), 1.32 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) 6 149.3, 136.4, 114.0, 83.2, 24.8; IR (film) 3450, 3358, 2927, 1628, 1359, ${1182},{1143},{860},{738}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${219}\left( {\mathrm{M}}^{ + }\right.$ , 65), 204 (16), 161 (13), 133 (22), 120 (77), 119 (100).
钯碳催化氢化反应的典型步骤。将4,4,5,5-四甲基-2-(4-硝基苯基)-1,3,2-二氧杂硼烷(2a，5 mmol，1.245 g)和钯碳(265 mg，0.25 mmol，[Pd/C] 10 wt%)在一个${100}\mathrm{\;{mL}}$反应管中称重。然后依次加入甲醇(25 mL)。所得反应溶液在室温下用一个${\mathrm{H}}_{2}$气球(1 atm)搅拌$4\mathrm{\;h}$。反应体系通过用二氯甲烷洗脱的硅胶过滤，然后反应混合物在减压下浓缩。粗残余物通过硅胶快速柱色谱法(PE/EA = 15:1)纯化，得到4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺${\left( 3a\right) }^{7b}$，分离产率为98%(1.071 g)，为浅黄色固体:$\mathrm{{mp}} = {148} - {150}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 7.62 $\left( {\mathrm{d}, J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{6.65}(\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}}$ (2H)，3.83(宽峰，2H)，1.32(s，12H)；${}^{13}\mathrm{C}$核磁共振(100 MHz，CDCl ${}_{3}$ )δ 149.3，136.4，114.0，83.2，24.8；红外光谱(薄膜)3450，3358，2927，1628，1359，${1182},{1143},{860},{738}{\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)${219}\left( {\mathrm{M}}^{ + }\right.$，65)，204(16)，161(13)，133(22)，120(77)，119(100)。
3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3b). ${}^{13}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 15:1, then 5:1) afforded 3b (1.02 g, 93%) as a white solid:mp $= {89} - {91}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.22-7.16 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.13}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.79} - {6.76}\left( {\mathrm{m},1\mathrm{H}}\right) ,{3.62}$ (br, 2H), 1.33 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 145.7, 128.7, 124.8, 121.0, 117.9, 83.6, 24.8; IR (film) 3466, 3377, 2981, 1628, 1444, 1359,1142,852,706 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 219 $\left( {{\mathrm{M}}^{ + }\text{ , }}\right.$ 85), 204 (19), 146 (11), 133 (37), 119 (100), 92 (13).
3-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺(3b)。${}^{13}$按照典型步骤进行操作，通过柱色谱法(硅胶，石油醚/乙酸乙酯 = 15:1，然后5:1)得到3b(1.02 g，93%)，为白色固体:熔点$= {89} - {91}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 7.22 - 7.16 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.13}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.79} - {6.76}\left( {\mathrm{m},1\mathrm{H}}\right) ,{3.62}$ (宽峰，2H)，1.33(s，12H)；${}^{13}\mathrm{C}$核磁共振(100 MHz，CDCl ${}_{3}$ )δ 145.7，128.7，124.8，121.0，117.9，83.6，24.8；红外光谱(薄膜)3466，3377，2981，1628，1444，1359，1142，852，706 ${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)219 $\left( {{\mathrm{M}}^{ + }\text{ , }}\right.$ 85)，204(19)，146(11)，133(37)，119(100)，92(13)。
3-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3c). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded 3c (1.03 g, 88%) as a yellow solid: mp $= {56} - {57}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ 7.59 (d, J = 8.6 Hz, 1H), 6.46-6.44 (m, 2H), 3.73 (br, 2H), 2.45 (s, 3H), 1.30 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.9,146.9,137.8,116.1,111.3,82.8,24.8,22.2; IR (film) 3375,2977,1601,1380,1348,1310,1146,1128,1061,860 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{233}\left( {{\mathrm{M}}^{ + },{67}}\right) ,{218}\left( 9\right) ,{175}\left( {13}\right) ,{160}}\right)$ (12), 148 (10), 133 (100), 106 (10); HRMS (ESI) calcd for ${\mathrm{C}}_{13}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{234.1662}$ , found 234.1656.
3-甲基-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺(3c)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到黄色固体3c(1.03 g，88%):熔点$= {56} - {57}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400 MHz，CDCl3)δ7.59(d，J = 8.6 Hz，1H)，6.46 - 6.44(m，2H)，3.73(br，2H)，2.45(s，3H)，1.30(s，12H)；${}^{13}\mathrm{C}$核磁共振(100 MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.9,146.9,137.8,116.1,111.3,82.8,24.8,22.2；红外光谱(薄膜)3375,2977,1601,1380,1348,1310,1146,1128,1061,860 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{233}\left( {{\mathrm{M}}^{ + },{67}}\right) ,{218}\left( 9\right) ,{175}\left( {13}\right) ,{160}}\right)$ (12)，148(10)，133(100)，106(10)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{13}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{234.1662}$ ，实测值为234.1656。
3-Chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3d). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded ${3d}\left( {{887}\mathrm{{mg}},{70}\% }\right)$ as a yellow solid: $\mathrm{{mp}} = {108} - {110}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.52 (d, $J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}$ ), ${6.63}(\mathrm{\;d}, J = \; {1.7}\mathrm{\;{Hz}},1\mathrm{H}),{6.49}\left( {\mathrm{\;{dd}}, J = {1.7},{8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.89}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.33}(\mathrm{\;s}$ , 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.9,141.1,138.2,115.3, 112.3, 83.4, 24.7; IR (film) 3381, 2979, 2925, 1601, 1352, 1311, 1142, 1107,907,732 ${\mathrm{{cm}}}^{-1}$ . EI-MS $\left( {m/z}\right.$ , relative intensity $){253}\left( {{\mathrm{M}}^{ + },{41}}\right)$ , 238 (11), 217 (25), 153 (100), 118 (8), 91 (13); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{\;B}}^{35}{\mathrm{{ClNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{254.1116}$ , found 254.1114.
3-氯-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺(3d)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到${3d}\left( {{887}\mathrm{{mg}},{70}\% }\right)$，为黄色固体:$\mathrm{{mp}} = {108} - {110}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 7.52(双峰，$J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}$)，${6.63}(\mathrm{\;d}, J = \; {1.7}\mathrm{\;{Hz}},1\mathrm{H}),{6.49}\left( {\mathrm{\;{dd}}, J = {1.7},{8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.89}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.33}(\mathrm{\;s}$，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 149.9,141.1,138.2,115.3,112.3,83.4,24.7；红外(薄膜)3381,2979,2925,1601,1352,1311,1142,1107,907,732 ${\mathrm{{cm}}}^{-1}$。电子轰击质谱$\left( {m/z}\right.$，相对强度$){253}\left( {{\mathrm{M}}^{ + },{41}}\right)$，238(11)，217(25)，153(100)，118(8)，91(13)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{\;B}}^{35}{\mathrm{{ClNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{254.1116}$，实测值为254.1114。
3-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3e). ${}^{14}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded 3e (861 mg, 73%) as a pale yellow solid: mp = 134- ${135}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) ${\delta 7.50}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.40} \; \left( {\mathrm{d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.29}\left( {\mathrm{\;d}, J = {11.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.95}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.32}(\mathrm{\;s}$ , 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 168.8 (d, $J = {248.9}\mathrm{\;{Hz}}$ ),151.6 $\left( {\mathrm{d}, J = {11.5}\mathrm{\;{Hz}}}\right) ,{137.9}\left( {\mathrm{\;d}, J = {10.6}\mathrm{\;{Hz}}}\right) ,{110.2}\left( {\mathrm{\;d}, J = {1.9}\mathrm{\;{Hz}}}\right) ,{101.0}$ (d, $J = {27.6}\mathrm{\;{Hz}}$ ),83.2,24.7; IR (film) 1629,1442,1357,1329,1133, ${908},{731}{\mathrm{\;{cm}}}^{-1}$ . EI-MS $\left( {m/z}\right.$ , relative intensity $){237}\left( {\mathrm{M}}^{ + }\right.$ ,37),222 (10), 177 (10), 164 (8), 152 (11), 137 (100), 92 (9); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{{BFNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{238.1411}$ , found 238.1409.
3-氟-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺(3e)。${}^{14}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 20:1，然后 10:1)得到 3e(861 mg，73%)，为浅黄色固体:熔点 = 134 - ${135}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振氢谱(400 MHz，${\mathrm{{CDCl}}}_{3}$ ) ${\delta 7.50}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.40} \; \left( {\mathrm{d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.29}\left( {\mathrm{\;d}, J = {11.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.95}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.32}(\mathrm{\;s}$ ，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100 MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 168.8(d，$J = {248.9}\mathrm{\;{Hz}}$ )，151.6 $\left( {\mathrm{d}, J = {11.5}\mathrm{\;{Hz}}}\right) ,{137.9}\left( {\mathrm{\;d}, J = {10.6}\mathrm{\;{Hz}}}\right) ,{110.2}\left( {\mathrm{\;d}, J = {1.9}\mathrm{\;{Hz}}}\right) ,{101.0}$ (d，$J = {27.6}\mathrm{\;{Hz}}$ )，83.2，24.7；红外光谱(薄膜)1629，1442，1357，1329，1133，${908},{731}{\mathrm{\;{cm}}}^{-1}$ 。电子轰击质谱 $\left( {m/z}\right.$ ，相对强度 $){237}\left( {\mathrm{M}}^{ + }\right.$ ，37)，222(10)，177(10)，164(8)，152(11)，137(100)，92(9)；高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{{BFNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{238.1411}$ ，实测值为 238.1409。
3-Bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3f). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded 3f (860 mg, 58%) as a yellow solid: mp $= {76} - {77}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.46 $\left( {\mathrm{d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.85}(\mathrm{\;d}, J = \; {1.6}\mathrm{\;{Hz}},1\mathrm{H}),{6.54}\left( {\mathrm{{dd}}, J = {1.6},{8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.85}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.33}(\mathrm{\;s}$ , 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.7,138.2,129.6,118.7, 112.8, 83.6, 24.7; IR (film) 3372, 2979, 1599, 1352, 1310, 1142, 1104, ${733}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) {297}\left( {{\mathrm{M}}^{ + },{47}}\right) ,{282}\left( {12}\right) ,{218}$ (31), 197 (100), 176 (25), 118 (45), 91 (44), 57 (33); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{\;B}}^{79}{\mathrm{{BrNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{298.0610}$ , found 298.0607.
3-溴-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺(3f)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到黄色固体3f(860mg，58%):熔点$= {76} - {77}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$7.46$\left( {\mathrm{d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.85}(\mathrm{\;d}, J = \; {1.6}\mathrm{\;{Hz}},1\mathrm{H}),{6.54}\left( {\mathrm{{dd}}, J = {1.6},{8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.85}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.33}(\mathrm{\;s}$，12H)；${}^{13}\mathrm{C}$核磁共振(100MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$149.7,138.2,129.6,118.7,112.8,83.6,24.7；红外光谱(薄膜)3372,2979,1599,1352,1310,1142,1104，${733}{\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity }}\right) {297}\left( {{\mathrm{M}}^{ + },{47}}\right) ,{282}\left( {12}\right) ,{218}$(31)，197(100)，176(25)，118(45)，91(44)，57(33)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{\;B}}^{79}{\mathrm{{BrNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{298.0610}$，实测值为298.0607。
5-Amino-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- benzonitrile (3g). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 5:1) afforded $3\mathbf{g}\left( {{891}\mathrm{{mg}},{73}\% }\right)$ as a yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.65 (d, $J = {8.2}\mathrm{{Hz}},1\mathrm{H}$ ),6.93 (d, $J = {2.3}\mathrm{\;{Hz}},1\mathrm{H}$ ), ${6.80}\left( {\mathrm{{dd}}, J = {2.3},{8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{4.14}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 149.1, 137.5, 119.2, 118.8, 118.4, 117.4, 84.1, 24.7; IR (film) 3369, 2980, 2232, 1602, 1452, 1355, 1330, 1145, 1121, ${853}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) {244}\left( {{\mathrm{M}}^{ + },{50}}\right) ,{229}\left( {18}\right) ,{201}$ (65), 186 (10), 144 (100), 118 (22), 91 (17); HRMS (ESI) calcd for ${\mathrm{C}}_{13}{\mathrm{H}}_{18}{\mathrm{{BN}}}_{2}{\mathrm{O}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{245.1458}$ , found 245.1454.
5-氨基-2-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯甲腈(3g)。按照典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后5:1)得到$3\mathbf{g}\left( {{891}\mathrm{{mg}},{73}\% }\right)$为黄色油状物:${}^{1}\mathrm{H}$核磁共振氢谱(400兆赫兹，氘代氯仿${}_{3}$) $\delta$ 7.65(双峰，$J = {8.2}\mathrm{{Hz}},1\mathrm{H}$) , 6.93(双峰，$J = {2.3}\mathrm{\;{Hz}},1\mathrm{H}$)，${6.80}\left( {\mathrm{{dd}}, J = {2.3},{8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{4.14}\left( {\mathrm{{br}},2\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振碳谱(100兆赫兹，氘代氯仿${}_{3}$) δ 149.1, 137.5, 119.2, 118.8, 118.4, 117.4, 84.1, 24.7；红外光谱(薄膜)3369, 2980, 2232, 1602, 1452, 1355, 1330, 1145, 1121, ${853}{\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity }}\right) {244}\left( {{\mathrm{M}}^{ + },{50}}\right) ,{229}\left( {18}\right) ,{201}$(65), 186(10), 144(100), 118(22), 91(17)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{13}{\mathrm{H}}_{18}{\mathrm{{BN}}}_{2}{\mathrm{O}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{245.1458}$，实测值为245.1454。
2-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3h). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded $3\mathbf{h}\left( {{995}\mathrm{{mg}},{84}\% }\right)$ as a pale yellow solid:mp $= {96} - {98} \; {}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.41-7.39 (m, $2\mathrm{H}$ ),6.74 (t, $J = \; {8.3}\mathrm{\;{Hz}},1\mathrm{H}),{3.91}$ (br, $2\mathrm{H}),{1.32}$ (s, ${12}\mathrm{H});{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 151.1 (d, $J = {239.2}\mathrm{\;{Hz}}$ ),137.5 (d, $J = {12.8}\mathrm{\;{Hz}}$ ),131.5 (d, $J =$ 3.0 Hz), 121.0 (d, J = 16.4 Hz), 115.9 (d, J = 3.0 Hz), 83.6, 24.8; IR (film) 3376,2979,1629,1428,1353,1313,1142,855,730 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{237}\left( {\mathrm{M}+,{53}}\right) ,{222}\left( {18}\right) ,{151}\left( {20}\right) ,{138}}\right)$ (50),137 (100),136 (20); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{{BFNO}}}_{2}$ [M + H]* 238.1411, found 238.1405.
2-氟-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺(3h)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到$3\mathbf{h}\left( {{995}\mathrm{{mg}},{84}\% }\right)$，为淡黄色固体:熔点$= {96} - {98} \; {}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 7.41 - 7.39(多重峰，$2\mathrm{H}$)，6.74(三重峰，$J = \; {8.3}\mathrm{\;{Hz}},1\mathrm{H}),{3.91}$(宽峰，$2\mathrm{H}),{1.32}$(单峰，${12}\mathrm{H});{}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 151.1(双峰，$J = {239.2}\mathrm{\;{Hz}}$)，137.5(双峰，$J = {12.8}\mathrm{\;{Hz}}$)，131.5(双峰，$J =$ 3.0赫兹)，121.0(双峰，J = 16.4赫兹)，115.9(双峰，J = 3.0赫兹)，83.6，24.8；红外(薄膜)3376,2979,1629,1428,1353,1313,1142,855,730 ${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{237}\left( {\mathrm{M}+,{53}}\right) ,{222}\left( {18}\right) ,{151}\left( {20}\right) ,{138}}\right)$(50)，137(100)，136(20)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{{BFNO}}}_{2}$ [M + H]* 238.1411，实测值为238.1405。
2-Chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3i). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded 3i (938 mg,74%) as a yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ 7.24 $\left( {\mathrm{d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.20}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.11}(\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}$ , 1H), 4.00 (br, 2H), 1.33 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta$ 142.3, 128.8, 125.2, 122.0, 115.3, 83.9, 24.8; IR (film) 3380, 2980, 1615,1418,1356,1144,1090,853,732 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative }}\right)$ intensity) ${253}\left( {{\mathrm{M}}^{ + },{46}}\right) ,{238}\left( {12}\right) ,{167}\left( {25}\right) ,{153}\left( {100}\right) ,{117}\left( {10}\right) ,{91}$ (15), 65 (10), 57 (14); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{\;B}}^{35}{\mathrm{{ClNO}}}_{2}$ [M + H] ${}^{ + }$ 254.1116, found 254.1109.
2-氯-5-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯胺(3i)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到3i(938毫克，74%)，为黄色油状物:${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3})\delta$ 7.24 $\left( {\mathrm{d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.20}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.11}(\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}$ ，1H)，4.00(宽峰，2H)，1.33(s，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl3) $\delta$ 142.3，128.8，125.2，122.0，115.3，83.9，24.8；红外光谱(薄膜)3380，2980，1615，1418，1356，1144，1090，853，732 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$\left( {m/z\text{ , relative }}\right)$强度) ${253}\left( {{\mathrm{M}}^{ + },{46}}\right) ,{238}\left( {12}\right) ,{167}\left( {25}\right) ,{153}\left( {100}\right) ,{117}\left( {10}\right) ,{91}$ (15)，65(10)，57(14)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{18}{\mathrm{\;B}}^{35}{\mathrm{{ClNO}}}_{2}$ [M + H] ${}^{ + }$ 254.1116，实测值为254.1109。
2-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3j). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded ${3j}\left( {{874}\mathrm{{mg}},{75}\% }\right)$ as a pale yellow solid:mp $= {107} - {108} \; {}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.16 (d, $J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}$ ),7.11 (s, 1H), 7.06 (d, J = 7.3 Hz, 1H), 3.46 (br, 2H), 2.17 (s, 3H), 1.32 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 144.0,129.9,125.8,125.2, 121.0, 83.5, 24.8, 17.5; IR (film) 3422, 3353, 2978, 1380, 1353, 1140, 856,686 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity $){233}\left( {{\mathrm{M}}^{ + },{100}),{218}}\right.$ (14), 174 (10), 160 (20), 147 (36), 133 (95), 132 (70), 106 (12); HRMS (ESI) calcd for ${\mathrm{C}}_{13}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{234.1662}$ , found 234.1655.
2-甲基-5-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯胺(3j)。按照典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到${3j}\left( {{874}\mathrm{{mg}},{75}\% }\right)$，为淡黄色固体:熔点$= {107} - {108} \; {}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.16(双峰，$J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}$ )，7.11(单峰，1H)，7.06(双峰，J = 7.3赫兹，1H)，3.46(宽峰，2H)，2.17(单峰，3H)，1.32(单峰，12H)；${}^{13}\mathrm{C}$ 核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 144.0，129.9，125.8，125.2，121.0，83.5，24.8，17.5；红外(薄膜)3422，3353，2978，1380，1353，1140，856，686 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$\left( {m/z}\right.$ ，相对强度$){233}\left( {{\mathrm{M}}^{ + },{100}),{218}}\right.$ (14)，174(10)，160(20)，147(36)，133(95)，132(70)，106(12)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{13}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{234.1662}$ ，实测值为234.1655。
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-1- amine (3k). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1, then 10:1) afforded 3k (1.08 g, 80%) as a pink solid: mp = 142-143 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 8.80 (d, $J = {8.4}\mathrm{\;{Hz}},1\mathrm{H}$ ),7.93 (d, $J = {7.5} \; \mathrm{{Hz}},1\mathrm{H}),{7.76}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.50}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.41}(\mathrm{t}, J =$ 7.5 Hz, 1H), 6.73 (d, J = 7.5 Hz, 1H), 4.32 (br, 2H), 1.38 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 145.4,138.2,137.2,129.2,126.4, 124.4, 123.0, 120.5, 108.6, 83.2, 24.9; IR (film) 3379, 2979, 1335, 1291,1271,1125,856,762 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 269 $\left( {{\mathrm{M}}^{ + },{100}}\right) ,{254}\left( 3\right) ,{210}\left( {10}\right) ,{196}\left( {40}\right) ,{184}\left( 8\right) ,{169}\left( {85}\right) ,{141}\left( {23}\right) , \; {127}\left( {14}\right) ,{115}\left( {23}\right)$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 270.1663, found 270.1660.
4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)萘-1-胺(3k)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到3k(1.08 g，80%)，为粉红色固体:熔点=142 - 143°C；${}^{1}\mathrm{H}$核磁共振(400兆赫，CDCl${}_{3}$)$\delta$8.80(双峰，$J = {8.4}\mathrm{\;{Hz}},1\mathrm{H}$)，7.93(双峰，$J = {7.5} \; \mathrm{{Hz}},1\mathrm{H}),{7.76}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.50}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.41}(\mathrm{t}, J =$7.5赫兹，1H)，6.73(双峰，J = 7.5赫兹，1H)，4.32(宽峰，2H)，1.38(单峰，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$)δ145.4，138.2，137.2，129.2，126.4，1２4.4，123.0，120.５，108.6，83.2，24.9；红外光谱(薄膜)3379，2979，1335，1291，1271，1125，856，762${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)269$\left( {{\mathrm{M}}^{ + },{100}}\right) ,{254}\left( 3\right) ,{210}\left( {10}\right) ,{196}\left( {40}\right) ,{184}\left( 8\right) ,{169}\left( {85}\right) ,{141}\left( {23}\right) , \; {127}\left( {14}\right) ,{115}\left( {23}\right)$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$270.1663，实测值为270.1660。
Typical Procedure for the Stannylation Reactions. Under a nitrogen atmosphere, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- aniline (3a,0.3 mmol,66 mg) and $\mathrm{{TsOH}} \cdot {\mathrm{H}}_{2}\mathrm{O}\left( {{0.36}\mathrm{{mmol}},{68}\mathrm{{mg}}}\right)$ were weighed in a ${10}\mathrm{\;{mL}}$ reaction tube. DCE (1.5 mL), $t$ -BuONO $\left( {{0.36}\mathrm{{mmol}},{37}\mathrm{{mg}}}\right)$ , and ${\left( {\mathrm{{SnMe}}}_{3}\right) }_{2}\left( {{0.33}\mathrm{{mmol}},{108}\mathrm{{mg}},{68\mu }\mathrm{L}}\right)$ were then added in succession. The resulting reaction solution was stirred for $4\mathrm{\;h}$ at $0{}^{ \circ }\mathrm{C}$ . The reaction mixture was then concentrated under reduced pressure, and the crude residue was purified by flash chromatography (PE/EA = 100:1). Trimethyl(4-(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl)phenyl)stannane ${\left( 4a\right) }^{7c}$ was obtained $({71}\mathrm{{mg}}$ , 65%) as a pale yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) $\delta$ 7.76 (d, $J = \; {7.5}\mathrm{\;{Hz}},2\mathrm{H}),{7.51}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.28}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 146.6, 135.2, 134.0, 83.6, 24.8, -9.6; IR (film) 2980,1594,1359,1144,1056,908,859,732 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 368 $\left( {{\mathrm{M}}^{ + },1}\right) ,{353}\left( {100}\right) ,{352}\left( {59}\right) ,{351}\left( {82}\right) ,{350}$ (48), 349 (50), 323 (11), 253 (10), 223 (11).
锡基化反应的典型步骤。在氮气气氛下，将4-(4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷-2-基)苯胺(3a，0.3 mmol，66 mg)和$\mathrm{{TsOH}} \cdot {\mathrm{H}}_{2}\mathrm{O}\left( {{0.36}\mathrm{{mmol}},{68}\mathrm{{mg}}}\right)$在${10}\mathrm{\;{mL}}$反应管中称重。然后依次加入1.5 mL二氯乙烷、$t$叔丁基亚硝酸酯$\left( {{0.36}\mathrm{{mmol}},{37}\mathrm{{mg}}}\right)$和${\left( {\mathrm{{SnMe}}}_{3}\right) }_{2}\left( {{0.33}\mathrm{{mmol}},{108}\mathrm{{mg}},{68\mu }\mathrm{L}}\right)$。所得反应溶液在$0{}^{ \circ }\mathrm{C}$下搅拌$4\mathrm{\;h}$。然后将反应混合物减压浓缩，粗残余物通过快速柱色谱法(石油醚/乙酸乙酯=100:1)纯化。得到浅黄色油状的三甲基(4-(4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷-2-基)苯基)锡烷${\left( 4a\right) }^{7c}$，产率$({71}\mathrm{{mg}}$，65%):${}^{1}\mathrm{H}$核磁共振氢谱(400 MHz，CDCl3)$\delta$ 7.76 (d，$J = \; {7.5}\mathrm{\;{Hz}},2\mathrm{H}),{7.51}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.28}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振碳谱(100 MHz，CDCl3)δ 146.6、135.2、134.0、83.6、24.8、-9.6；红外光谱(薄膜)2980、1594、1359、1144、1056、908、859、732${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)368$\left( {{\mathrm{M}}^{ + },1}\right) ,{353}\left( {100}\right) ,{352}\left( {59}\right) ,{351}\left( {82}\right) ,{350}$(48)、349(50)、323(11)、253(10)、223(11)。
Trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- phenyl)stannane (4b). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1) afforded 4b ( ${53}\mathrm{{mg}},{48}\%$ ) as a yellow liquid: ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}){\delta 7.93}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.76}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.59}(\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}$ , 1H), 7.37-7.33 (m, 1H), 1.35 (s, 12H), 0.29 (s, 9H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 142.1, 141.4, 138.7, 134.7, 127.4, 83.7, 24.8, -9.5; IR (film) 2980, 2361, 1588, 1354, 1310, 1145, 1096, 910, 862, 753 cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 368 (M }{}^{ + },2}\right) ,{353}$ (100),351 (80),349 (48), 323 (12), 265 (5), 253 (11), 237 (5), 223 (13); HRMS (ESI) calcd for ${\mathrm{C}}_{14}{\mathrm{H}}_{22}{\mathrm{{BO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} - {\mathrm{{CH}}}_{3}\right\rbrack }^{ + }$ 353.0734, found 353.0729.
三甲基(3-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-苯基)锡烷(4b)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 100:1)得到黄色液体4b(${53}\mathrm{{mg}},{48}\%$):${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}){\delta 7.93}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.76}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.59}(\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}$，1H)，7.37 - 7.33(多重峰，1H)，1.35(单峰，12H)，0.29(单峰，9H);${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl${}_{3}$)$\delta$142.1，141.4，138.7，134.7，127.4，83.7，24.8，-9.5;红外(薄膜)2980，2361，1588，1354，1310，1145，1096，910，862，753厘米${}^{-1}$;电子轰击质谱$\left( {m/z\text{ , relative intensity) 368 (M }{}^{ + },2}\right) ,{353}$(100)，351(80)，349(48)，323(12)，265(5)，253(11)，237(5)，223(13);高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{14}{\mathrm{H}}_{22}{\mathrm{{BO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} - {\mathrm{{CH}}}_{3}\right\rbrack }^{ + }$353.0734，实测值为353.0729。
Trimethyl(3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl)stannane (4c). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether, then petroleum ether/EtOAc = 100:1) afforded 4c (65 mg, 57%) as a yellow solid: $\mathrm{{mp}} = {92} - {94}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.72 (d, $J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}),{7.31} - {7.29}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{2.53}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.27}$ (s, 9H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 145.9, 144.0, 137.3, 135.1, 132.2, 83.3, 24.9, 22.2, -9.7; IR (film) 2979, 1587, 1373, 1344, 1313, 1145,1060,909,792 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) {367}(\lbrack \mathrm{M} -$ 15] ${}^{ + }$ ,100),337 (13),267 (15),235 (17),207 (6),134 (10),117 (8), 57 (9); HRMS (ESI) calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{27}{\mathrm{{BNaO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$ 405.1024, found 405.1013.
三甲基(3-甲基-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)锡烷(4c)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚，然后石油醚/乙酸乙酯=100:1)得到黄色固体状的4c(65mg，57%):$\mathrm{{mp}} = {92} - {94}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$7.72(d，$J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}),{7.31} - {7.29}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{2.53}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.27}$(s，9H)；${}^{13}\mathrm{C}$核磁共振(100MHz，CDCl${}_{3}$)δ145.9，144.0，137.3，135.1，132.2，83.3，24.9，22.2，-9.7；红外光谱(薄膜)2979，1587，1373，1344，1313，1145，1060，909，792${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity }}\right) {367}(\lbrack \mathrm{M} -$15]${}^{ + }$，100)，337(13)，267(15)，235(17)，207(6)，134(10)，117(8)，57(9)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{27}{\mathrm{{BNaO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$405.1024，实测值为405.1013。
(3-Chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- phenyl)trimethylstannane (4d). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether, then petroleum ether/EtOAc = 50:1) afforded 4d (89 mg, 74%) as a yellow solid: $\mathrm{{mp}} = {67} - {69}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) ${\delta 7.65}\left( {\mathrm{\;d}, J = {7.1}}\right. \; \mathrm{{Hz}},1\mathrm{H}),{7.47}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.35}\left( {\mathrm{\;d}, J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.39}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.32}(\mathrm{\;s}$ , 9H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.0,139.5,136.2,135.7, 133.0, 84.0, 24.8, -9.5; IR (film) 2980, 1583, 1366, 1344, 1320, 1143, 1037,908,733 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity $){387}({\left\lbrack \mathrm{M} - {15}\right\rbrack }^{ + }$ , 100), 385 (75), 384 (38), 287 (10), 257 (7), 165 (7), 135 (8); HRMS (ESI) calcd for ${\mathrm{C}}_{15}{\mathrm{H}}_{24}{\mathrm{\;B}}^{35}{\mathrm{{ClNaO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }{425.0470}$ , found 425.0481.
(3-氯-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-苯基)三甲基锡烷(4d)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚，然后石油醚/乙酸乙酯=50:1)得到黄色固体4d(89mg，产率74%):$\mathrm{{mp}} = {67} - {69}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)${\delta 7.65}\left( {\mathrm{\;d}, J = {7.1}}\right. \; \mathrm{{Hz}},1\mathrm{H}),{7.47}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.35}\left( {\mathrm{\;d}, J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.39}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.32}(\mathrm{\;s}$，9H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$148.0、139.5、136.2、135.7、133.0、84.0、24.8、-9.5；红外光谱(薄膜)2980、1583、1366、1344、1320、1143、1037、908、733${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度$){387}({\left\lbrack \mathrm{M} - {15}\right\rbrack }^{ + }$，100)，385(75)，384(38)；287(10)，257(7)，165(7)，135(8)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{15}{\mathrm{H}}_{24}{\mathrm{\;B}}^{35}{\mathrm{{ClNaO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }{425.0470}$，实测值为425.0481。
(3-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)- trimethylstannane (4e). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 4e (102 mg,88%) as a yellow solid: $\mathrm{{mp}} = {64} - {65}{}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.73-7.70 (m,1H),7.27 (d, $J = {7.6} \; \mathrm{{Hz}},1\mathrm{H}),{7.19}\left( {\mathrm{\;d}, J = {8.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.38}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.33}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 166.7 (d, J = 255.4 Hz), 150.0 (d, J = 3.8 $\mathrm{{Hz}}),{135.9}\left( {\mathrm{\;d}, J = {6.6}\mathrm{\;{Hz}}}\right) ,{130.9}\left( {\mathrm{\;d}, J = {3.2}\mathrm{\;{Hz}}}\right) ,{122.1}(\mathrm{\;d}, J = {20.5}$ Hz), 83.8, 24.8, -9.5; IR (film) 2980, 1728, 1605, 1384, 1352, 1137, ${1054},{908},{733}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${371}\left( {\left\lbrack \mathrm{M} - {15}\right\rbrack }^{ + }\right.$ , 100), 341 (9), 271 (10), 241 (10), 165 (9), 134 (11); HRMS (ESI) calcd for ${\mathrm{C}}_{15}{\mathrm{H}}_{25}{\mathrm{{BFO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 387.0953, found 387.0961.
(3-氟-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼戊环-2-基)苯基)-三甲基锡烷 (4e)。按照典型操作步骤进行，经快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1)分离得到 4e(102 mg，88%)，为黄色固体:$\mathrm{{mp}} = {64} - {65}{}^{ \circ }\mathrm{C}$ ； ${}^{1}\mathrm{H}$ 核磁共振谱(400 MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.73 - 7.70 (m, 1H)，7.27 (d, $J = {7.6} \; \mathrm{{Hz}},1\mathrm{H}),{7.19}\left( {\mathrm{\;d}, J = {8.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.38}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.33}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振谱(100 MHz，CDCl ${}_{3}$ )δ 166.7 (d, J = 255.4 Hz)，150.0 (d, J = 3.8 $\mathrm{{Hz}}),{135.9}\left( {\mathrm{\;d}, J = {6.6}\mathrm{\;{Hz}}}\right) ,{130.9}\left( {\mathrm{\;d}, J = {3.2}\mathrm{\;{Hz}}}\right) ,{122.1}(\mathrm{\;d}, J = {20.5}$ Hz)，83.8，24.8， -9.5；红外光谱(薄膜)2980，1728，1605，1384，1352，1137， ${1054},{908},{733}{\mathrm{\;{cm}}}^{-1}$ ；电子轰击质谱 $(m/z$ ，相对强度) ${371}\left( {\left\lbrack \mathrm{M} - {15}\right\rbrack }^{ + }\right.$ ，100)，341 (9)，271 (10)，241 (10)，165 (9)，134 (11)；高分辨质谱(电喷雾电离)计算值 ${\mathrm{C}}_{15}{\mathrm{H}}_{25}{\mathrm{{BFO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 387.0953，实测值 387.0961。
(3-Bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- phenyl)trimethylstannane (4f). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 4f (96mg,72%) as a yellow solid: mp = 70-71 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.66 (s,1H),7.58 (d, $J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}$ ), ${7.40}\left( {\mathrm{\;d}, J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.39}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.32}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}$ (100 MHz, CDCl3) δ 148.2, 139.3, 135.7, 133.4, 128.6, 84.2, 24.8, -9.5; IR (film) 2980, 1578, 1363, 1344, 1319, 1144, 1027, 859, 771 cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 446 }\left( {{\mathrm{M}}^{ + },2}\right) ,{431}\left( {100}\right) ,{401}\left( 6\right) ,{331}}\right)$ (13), 301 (7), 199 (11), 165 (9), 135 (8); HRMS (ESI) calcd for ${\mathrm{C}}_{15}{\mathrm{H}}_{25}{\mathrm{\;B}}^{79}{\mathrm{{BrO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{447.0142}$ , found447.0155.
(3-溴-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)三甲基锡(4f)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1)得到4f(96mg，72%)，为黄色固体:熔点 = 70 - 71 °C；${}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 7.66(s，1H)，7.58(d，$J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}$)，${7.40}\left( {\mathrm{\;d}, J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.39}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.32}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}$(100 MHz，CDCl3)δ 148.2，139.3，135.7，133.4，128.6，84.2，24.8，-9.5；红外(薄膜)2980，1578，1363，1344，1319，1144，1027，859，771 cm ${}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) 446 }\left( {{\mathrm{M}}^{ + },2}\right) ,{431}\left( {100}\right) ,{401}\left( 6\right) ,{331}}\right)$(13)，301(7)，199(11)，165(9)，135(8)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{15}{\mathrm{H}}_{25}{\mathrm{\;B}}^{79}{\mathrm{{BrO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{447.0142}$，实测值447.0155。
2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-5- (trimethylstannyl)benzonitrile (4g). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 4g (53 mg, 45%) as a yellow liquid: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.81-7.79 (m, 2H), 7.67 (d, J = 7.9 Hz, 1H), 1.38 (s, 12H), 0.33 (s, 9H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta$ 147.3, 140.5, 138.8, 134.6, 116.7, 84.6, 24.8, -9.5; IR (film) 2930, 2228,1373,1288,1138,909,734 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${393}\left( {{\mathrm{M}}^{ + },2}\right) ,{378}\left( {100}\right) ,{376}\left( {75}\right) ,{374}\left( {46}\right) ,{278}\left( {10}\right) ,{245}$ (10),134 (9); HRMS (ESI) calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{25}{\mathrm{{BNO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 394.1000, found 394.1003.
2-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-5-(三甲基锡基)苯甲腈(4g)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1)得到4g(53 mg，45%)，为黄色液体:${}^{1}\mathrm{H}$核磁共振(400 MHz，CDCl ${}_{3}$)$\delta$ 7.81 - 7.79(m，2H)，7.67(d，J = 7.9 Hz，1H)，1.38(s，12H)，0.33(s，9H)；${}^{13}\mathrm{C}$核磁共振(100 MHz，CDCl3)$\delta$ 147.3，140.5，138.8，134.6，116.7，84.6，24.8，-9.5；红外(薄膜)2930，2228，1373，1288，1138，909，734 ${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)${393}\left( {{\mathrm{M}}^{ + },2}\right) ,{378}\left( {100}\right) ,{376}\left( {75}\right) ,{374}\left( {46}\right) ,{278}\left( {10}\right) ,{245}$(10)，134(9)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{25}{\mathrm{{BNO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 394.1000，实测值394.1003。
(2-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)- trimethylstannane (4h). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 4h ( ${79}\mathrm{{mg}},{68}\%$ ) as a yellow solid: $\mathrm{{mp}} = {90} - {91}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ 7.56-7.53 (m, 1H), 7.42-7.40 (m, 2H), ${1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.34}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 165.2 (d, $J = {234.1}\mathrm{\;{Hz}}),{131.0}\left( {\mathrm{\;d}, J = {26.5}\mathrm{\;{Hz}}}\right) ,{136.3}\left( {\mathrm{\;d}, J = {14.0}\mathrm{\;{Hz}}}\right) ,{130.1}(\mathrm{\;d}$ , $J = {2.4}\mathrm{\;{Hz}}),{119.6}\left( {\mathrm{\;d}, J = {25.6}\mathrm{\;{Hz}}}\right) ,{84.0},{24.8}, - {9.2}$ ; IR (film) 2980, 1727,1389,1355,1144,908,734 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) 371 ([M - 15]*, 100), 369 (79), 368 (46), 269 (13), 225 (15),169 (13),135 (21); HRMS (ESI) calcd for ${\mathrm{C}}_{15}{\mathrm{H}}_{24}{\mathrm{{BFNaO}}}_{2}{}^{120}\mathrm{{Sn}} \; {\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$ 409.0772, found 409.0780.
(2-氟-4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-三甲基锡烷(4h)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1)得到黄色固体4h(${79}\mathrm{{mg}},{68}\%$):$\mathrm{{mp}} = {90} - {91}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振氢谱(400兆赫兹，CDCl3)δ 7.56 - 7.53(多重峰，1H)，7.42 - 7.40(多重峰，2H)，${1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{0.34}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振碳谱(100兆赫兹，CDCl${}_{3}$)$\delta$ 165.2(双峰，$J = {234.1}\mathrm{\;{Hz}}),{131.0}\left( {\mathrm{\;d}, J = {26.5}\mathrm{\;{Hz}}}\right) ,{136.3}\left( {\mathrm{\;d}, J = {14.0}\mathrm{\;{Hz}}}\right) ,{130.1}(\mathrm{\;d}$，$J = {2.4}\mathrm{\;{Hz}}),{119.6}\left( {\mathrm{\;d}, J = {25.6}\mathrm{\;{Hz}}}\right) ,{84.0},{24.8}, - {9.2}$；红外光谱(薄膜)2980，1727，1389，1355，1144，908，734${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度)371([M - 15]*，100)，369(79)，368(46)，269(13)，225(15)，l69(13)，135(21)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{15}{\mathrm{H}}_{24}{\mathrm{{BFNaO}}}_{2}{}^{120}\mathrm{{Sn}} \; {\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$ 409.0772，实测值为409.0780。
(2-Chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- phenyl)trimethylstannane (4i). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 4i (43 mg, 36%) as a yellow liquid: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.81 (d, $J =$ 1.4 Hz, 1H), 7.68 (dd, $J =$ 1.4, 7.9 Hz, 1H), 7.32 (d, $J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}$ ), 1.33 (s, 12H), 0.37 (s, 9H); ${}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 146.0},{143.3},{141.8},{136.5},{127.6},{83.9},{24.8}$ , -8.3; IR (film) 2982, 1597, 1394, 1360, 1145, 1095, 734 cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{387}\left( {{\left\lbrack \mathrm{M} - {15}\right\rbrack }^{ + },{100}}\right) ,{287}\left( {22}\right) ,{255}({17}}\right)$ , 217 (30), 185 (52), 155 (35), 135 (26), 59 (33); HRMS (ESI) calcd for ${\mathrm{C}}_{15}{\mathrm{H}}_{24}{\mathrm{\;B}}^{35}{\mathrm{{ClNaO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }{425.0470}$ , found425.0487.
(2-氯-5-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)三甲基锡烷(4i)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1)得到4i(43毫克，产率36%)，为黄色液体:${}^{1}\mathrm{H}$核磁共振(400兆赫兹，CDCl${}_{3}$)$\delta$7.81(双峰，$J =$1.4赫兹，1H)，7.68(双重峰，$J =$1.4，7.9赫兹，1H)，7.32(双峰，$J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}$)，1.33(单峰，12H)，0.37(单峰，9H)；${}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 146.0},{143.3},{141.8},{136.5},{127.6},{83.9},{24.8}$， -8.3；红外光谱(薄膜)2982，1597，1394，1360，1145，1095，734厘米${}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{387}\left( {{\left\lbrack \mathrm{M} - {15}\right\rbrack }^{ + },{100}}\right) ,{287}\left( {22}\right) ,{255}({17}}\right)$，217(30)，185(52)，155(35)，135(26)，59(33)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{15}{\mathrm{H}}_{24}{\mathrm{\;B}}^{35}{\mathrm{{ClNaO}}}_{2}{}^{120}\mathrm{{Sn}}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }{425.0470}$，实测值425.0487。
2,2’-(4-Chloro-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxa-borolane) (4i’). The typical procedure of borylation was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1, then 50:1) afforded $4{i}^{\prime }\left( {{72}\mathrm{{mg}},{66}\% }\right)$ as a yellow solid: $\mathrm{{mp}} =$ 70-71 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 8.09 (d, $J = {1.7}\mathrm{\;{Hz}},1\mathrm{H}$ ), ${7.75}\left( {\mathrm{{dd}}, J = {1.7},{8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.34}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right)$ , 1.34 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 142.8, 142.6, 138.1, 128.7, 84.1, 83.9, 24.8; IR (film) 2980, 1593, 1358, 1328, 1143, 1113, ${848},{732}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity $){364}\left( {{\mathrm{M}}^{ + },{15}),{349}}\right.$ (28), 329 (100), 265 (51), 249 (30), 165 (34), 83 (36), 59 (46); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{28}{\mathrm{\;B}}_{2}{}^{35}{\mathrm{{ClO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{365.1864}$ , found 365.1858.
2,2’-(4-氯-1,3-亚苯基)双(4,4,5,5-四甲基-1,3,2-二氧杂硼戊环)(4i’)。按照硼氢化反应的典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1，然后50:1)得到$4{i}^{\prime }\left( {{72}\mathrm{{mg}},{66}\% }\right)$为黄色固体:$\mathrm{{mp}} =$ 70 - 71℃；${}^{1}\mathrm{H}$核磁共振(400兆赫兹，CDCl${}_{3}$)$\delta$ 8.09(d，$J = {1.7}\mathrm{\;{Hz}},1\mathrm{H}$)，${7.75}\left( {\mathrm{{dd}}, J = {1.7},{8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.34}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right)$，1.34(s，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫兹，CDCl${}_{3}$)δ 142.8，142.6，138.1，128.7，84.1，83.9，24.8；红外光谱(薄膜)2980，1593，1358，1328，1143，1113，${848},{732}{\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度$){364}\left( {{\mathrm{M}}^{ + },{15}),{349}}\right.$(28)，329(100)，265(51)，249(30)，165(34)，83(36)，59(46)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{28}{\mathrm{\;B}}_{2}{}^{35}{\mathrm{{ClO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{365.1864}$，实测值为365.1858。
2,2’-(4-Methyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxa-borolane) (4j). The typical procedure of borylation was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1, then 100:1) afforded 4j (52 mg, 50%) as a white solid: mp = ${102} - {103}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.19 (s,1H),7.75 (d, $J = \; {7.5}\mathrm{\;{Hz}},1\mathrm{H}),{7.16}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.54}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{24}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 148.2, 142.3, 137.3, 129.2, 83.6, 83.4, 24.9, 24.8, 22.5; IR (film) 2918, 1603, 1361, 1323, 1142, 908, 732 cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 344 (M }{}^{ + }\text{ ,37),329 (49),287 (100),258 }}\right)$ (31), 245 (78), 229 (57), 145 (64), 83 (41), 59 (41); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{31}{\mathrm{\;B}}_{2}{\mathrm{O}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 345.2409, found 345.2416.
2,2’-(4-甲基-1,3-亚苯基)双(4,4,5,5-四甲基-1,3,2-二氧杂硼戊环)(4j)。按照硼氢化反应的典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1，然后100:1)得到白色固体4j(52mg，产率50%):熔点=${102} - {103}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$8.19(单峰，1H)，7.75(双峰，$J = \; {7.5}\mathrm{\;{Hz}},1\mathrm{H}),{7.16}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.54}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{24}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100MHz，CDCl${}_{3}$)δ148.2、142.3、137.3、129.2、83.6、83.4、24.9、24.8、22.5；红外光谱(薄膜)2918、1603、1361、1323、1142、908、732cm${}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) 344 (M }{}^{ + }\text{ ,37),329 (49),287 (100),258 }}\right)$(31)，245(78)，229(57)，145(64)，83(41)，59(41)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{31}{\mathrm{\;B}}_{2}{\mathrm{O}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$345.2409，实测值为345.2416。
1,4-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalene (4k). The typical procedure of borylation was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1, then 100:1) afforded 4k (48 mg, 42%) as an orange solid:mp = 162- ${163}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.75 (dd, $J = {3.4},{6.4}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${8.02}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{7.51}\left( {\mathrm{\;{dd}}, J = {3.4},{6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.42}\left( {\mathrm{\;s},{24}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 136.5, 134.3, 128.6, 125.8, 83.8, 24.9; IR (film) 2978, 2925, 1726, 1461, 1339, 1260, 1135, 909, 733 cm ${}^{-1}$ ; EI-MS (m/ $z$ , relative intensity) ${380}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{365}\left( {13}\right) ,{295}\left( {14}\right) ,{280}\left( {24}\right) ,{265}$ (22), 194 (19), 180 (28), 101 (23), 83 (30), 59 (40); HRMS (ESI) calcd for ${\mathrm{C}}_{22}{\mathrm{H}}_{31}{\mathrm{\;B}}_{2}{\mathrm{O}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 381.2410, found 381.2408.
1,4-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)萘(4k)。按照硼化反应的典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1，然后100:1)得到橙色固体4k(48mg，产率42%):熔点=162 - ${163}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振(400MHz，CDCl ${}_{3}$ )δ8.75(dd，$J = {3.4},{6.4}\mathrm{\;{Hz}},2\mathrm{H}$ )，${8.02}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{7.51}\left( {\mathrm{\;{dd}}, J = {3.4},{6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.42}\left( {\mathrm{\;s},{24}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100MHz，CDCl3)δ136.5、134.3、128.6、125.8、83.8、24.9；红外光谱(薄膜)2978、2925、1726、1461、1339、1260、1135、909、733cm ${}^{-1}$ ；电子轰击质谱(m/$z$ ，相对强度)${380}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{365}\left( {13}\right) ,{295}\left( {14}\right) ,{280}\left( {24}\right) ,{265}$ (22)、194(19)、180(28)、101(23)、83(30)、59(40)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{22}{\mathrm{H}}_{31}{\mathrm{\;B}}_{2}{\mathrm{O}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 381.2410，实测值为381.2408。
Typical Procedure for the Chemoselective Stille Cross-Coupling Reactions. Under a nitrogen atmosphere, trimethyl(4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)stannane (4a, 0.5 mmol, 184 mg), methyl 4-bromobenzoate (0.5 mmol, 108 mg), $\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{0.025}\mathrm{{mmol}},{29}\mathrm{{mg}}}\right)$ , and toluene $\left( {3\mathrm{\;{mL}}}\right)$ were weighed in a ${10}\mathrm{\;{mL}}$ round-bottom flask. The reaction mixture was stirred for ${12}\mathrm{\;h}$ at ${110}^{ \circ }\mathrm{C}$ . The solution was then cooled down to room temperature and concentrated under reduced pressure. The crude residue was purified by silica gel flash column chromatography (petroleum ether/ EtOAc = 50:1) to give methyl 4’-(4,4,5,5-tetramethyl-1,3,2-dioxabor-olan-2-yl)biphenyl-4-carboxylate (5a) in 93% isolated yield (158 mg) as a white solid: mp 123-124 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.10 $\left( {\mathrm{d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.91}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.68}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.63}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.94}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 166.9, 145.4, 142.5, 135.3, 130.1, 129.1, 127.1, 126.5, 83.9, 52.1, 24.9; IR (film) 2976, 1718, 1610, 1361, 1288, 1273, 1148, 1093,737 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity $){338}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{323}$ (45), 307 (15), 252 (79), 239 (78), 207 (58), 178 (27), 152 (20); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 339.1766, found 339.1762.
化学选择性Stille交叉偶联反应的典型步骤。在氮气气氛下，将三甲基(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)锡烷(4a，0.5 mmol，184 mg)、4-溴苯甲酸甲酯(0.5 mmol，108 mg)、$\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{0.025}\mathrm{{mmol}},{29}\mathrm{{mg}}}\right)$和甲苯$\left( {3\mathrm{\;{mL}}}\right)$在一个${10}\mathrm{\;{mL}}$圆底烧瓶中称重。反应混合物在${110}^{ \circ }\mathrm{C}$搅拌${12}\mathrm{\;h}$。然后将溶液冷却至室温并在减压下浓缩。粗残余物通过硅胶快速柱色谱法(石油醚/乙酸乙酯 = 50:1)纯化，得到4’-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)联苯-4-羧酸甲酯(5a)，分离产率为93%(158 mg)，为白色固体:熔点123 - 124 °C；${}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$)δ 8.10 $\left( {\mathrm{d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.91}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.68}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right)$，${7.63}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.94}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100 MHz，CDCl${}_{3}$) $\delta$ 166.9、145.4、142.5、135.3、130.1、129.1、127.1、126.5、83.9、52.1、24.9；红外光谱(薄膜)2976、1718、1610、1361、1288、1273、1148、1093、737 ${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度$){338}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{323}$(45)、307(15)、252(79)、239(78)、207(58)、178(27)、152(20)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 339.1766，实测值为339.1762。
4,4,5,5-Tetramethyl-2-(4’-(trifluoromethyl)biphenyl-4-yl)-1,3,2-di-oxaborolane (5b). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1, then 50:1) afforded 5b (165 mg, 95%) as a white solid: mp = 96-98 ${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.83 (d, $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.62- ${7.59}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.52}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.28}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 144.5,142.3,135.4,129.6 $\left( {\mathrm{q}, J = {32.4}\mathrm{\;{Hz}}}\right)$ ,127.5, 126.5,125.7 $\left( {\mathrm{q}, J = {3.7}\mathrm{\;{Hz}}}\right) ,{124.0}\left( {\mathrm{q}, J = {270}\mathrm{\;{Hz}}}\right) ,{83.9},{24.9}$ ; IR (film) 2980,1361,1325,1144,1126,1071,824 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 348 (M ${}^{ + }$ , 63), 333 (48), 262 (78), 248 (100), 229 (13), 201 (9), 178 (9), 153(8); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{BF}}}_{3}{\mathrm{O}}_{2} \; {\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 349.1585, found 349.1592.
4,4,5,5-四甲基-2-(4’-(三氟甲基)联苯-4-基)-1,3,2-二氧杂硼烷(5b)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1，然后50:1)得到白色固体5b(165mg，95%):熔点=96 - 98${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$7.83(d，$J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}$)，7.62 - ${7.59}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.52}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.28}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$144.5,142.3,135.4,129.6$\left( {\mathrm{q}, J = {32.4}\mathrm{\;{Hz}}}\right)$，127.5,126.5,125.7$\left( {\mathrm{q}, J = {3.7}\mathrm{\;{Hz}}}\right) ,{124.0}\left( {\mathrm{q}, J = {270}\mathrm{\;{Hz}}}\right) ,{83.9},{24.9}$；红外光谱(薄膜)2980,1361,1325,1144,1126,1071,824${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)348(M${}^{ + }$，63)，333(48)，262(78)，248(100)，229(13)，201(9)，178(9)，153(8)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{BF}}}_{3}{\mathrm{O}}_{2} \; {\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$349.1585，实测值为349.1592。
1-(4’-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-3- yl)ethanone (5c). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 15:1) afforded 5c (121 mg,75%) as a yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.20 (s, 1H), 7.94-7.90 (m, 3H), 7.80 (d, J = 7.7 Hz, 1H), ${7.63}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.53}\left( {\mathrm{t}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.65}\left( {\mathrm{\;s},3\mathrm{H}}\right)$ , ${1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 197.9},{142.7},{141.5}$ , 137.6, 135.3, 131.7, 129.0, 127.4, 126.9, 126.4, 83.8, 26.7, 24.8; IR (film) 2979, 1686, 1610, 1397, 1360, 1234, 1144, 1093, 733 cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{322}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{307}\left( {57}\right) ,{236}\left( {88}\right) ,{223}}\right)$ (64), 207 (77), 179 (34), 152 (22); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{3} \; {\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 323.1817, found 323.1822.
1-(4’-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)联苯-3-基)乙酮(5c)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后15:1)得到5c(121mg，75%)，为黄色油状物:${}^{1}\mathrm{H}$核磁共振(400MHz，CDCl${}_{3}$)δ8.20(s，1H)，7.94 - 7.90(m，3H)，7.80(d，J = 7.7Hz，1H)，${7.63}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.53}\left( {\mathrm{t}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.65}\left( {\mathrm{\;s},3\mathrm{H}}\right)$，${1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 197.9},{142.7},{141.5}$，137.6，135.3，131.7，129.0，127.4，126.9，126.4，83.8，26.7，24.8；红外光谱(薄膜)2979，1686，1610，1397，1360，1234，1144，1093，733cm${}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{322}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{307}\left( {57}\right) ,{236}\left( {88}\right) ,{223}}\right)$(64)，207(77)，179(34)，152(22)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{3} \; {\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$323.1817，实测值为323.1822。
4’-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-3-car-baldehyde (5d). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 25:1) afforded 5d (139 mg,90%) as a yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ 10.08 (s,1H),8.11 (s,1H),7.92 (d, $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.88} - \; {7.85}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.64}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.60}\left( {\mathrm{t}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.37}$ (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl, 3) 6 192.2, 142.2, 141.9, 136.9, 135.4, 133.0, 129.5, 128.8, 128.2, 126.3, 83.9, 24.8; IR (film) 2978, 1700,1610,1398,1360,1144,1093,859 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 308 (M ${}^{ + }$ , 100), 293 (52), 222 (100), 209 (81), 208 (81), 207 (67), 179 (31), 152 (24); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{22}{\mathrm{{BO}}}_{3}$ [M + H]* 309.1660, found 309.1661.
4’-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)联苯-3-甲醛(5d)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后25:1)得到5d(139mg，90%)，为黄色油状物:${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3})\delta$ 10.08(单峰，1H)，8.11(单峰，1H)，7.92(双峰，$J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.88} - \; {7.85}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.64}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.60}\left( {\mathrm{t}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.37}$ (单峰，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl，3)δ192.2，142.2，141.9，136.9，135.4，133.0，129.5，128.8，128.2，126.3，83.9，24.8；红外光谱(薄膜)2978，1700，1610，1398，1360，1144，1093，859 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$(m/z$ ，相对强度)308(M ${}^{ + }$ ，100)，293(52)，222(100)，209(81)，208(81)，207(67)，179(31)，152(24)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{22}{\mathrm{{BO}}}_{3}$ [M + H]* 309.1660，实测值为309.1661。
4’-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-3-car-bonitrile (5e). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 40:1) afforded 5e (115 mg,75%) as a yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.92 $\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.88}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.83}(\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}$ , 1H), 7.63 (d, J = 7.8 Hz, 1H), 7.57 (d, J = 8.1 Hz, 2H), 7.55-7.52 (m, 1H), 1.37 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl, 3) 6 142.2, 141.3, 135.5, 131.5, 130.9, 130.7, 129.6, 126.3, 118.7, 113.0, 84.0, 24.8; IR (film) 2979, 2231, 1728, 1611, 1361, 1144, 1093, 733 cm ${}^{-1}$ ; EI-MS $\left( {m/z,\text{ relative intensity) }{305}\left( {{\mathrm{M}}^{ + },{63}}\right) ,{290}\left( {62}\right) ,{219}\left( {88}\right) ,{205}\left( {100}\right) ,}\right)$ 177 (19), 151 (11), 85 (10), 59 (100); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{306.1663}$ , found 306.1668.
4’-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)联苯-3-甲腈(5e)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后40:1)得到5e(115mg，75%)，为黄色油状物:${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 7.92 $\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.88}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.83}(\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}$，1H)，7.63(双峰，J = 7.8赫兹，1H)，7.57(双峰，J = 8.1赫兹，2H)，7.55 - 7.52(多重峰，1H)，1.37(单峰, 12H); ${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl, 3) 6 142. 的2, 141.3, 135.5, 131.5, 130.9, 130.7, 129.6, 126.3, 118.7, 113.0, 84.0, 24.8; 红外(薄膜) 2979, 2231, 1728, 1611, 1361, 1144, 1093, 733厘米${}^{-1}$; 电子轰击质谱$\left( {m/z,\text{ relative intensity) }{305}\left( {{\mathrm{M}}^{ + },{63}}\right) ,{290}\left( {62}\right) ,{219}\left( {88}\right) ,{205}\left( {100}\right) ,}\right)$ 177(19), 151(11), 85(10), 59(100); 高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{306.1663}$，实测值为306.1668。
2-(Biphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5f). ${}^{7b}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1, then 50:1) afforded 5f $\left( {{128}\mathrm{{mg}},{91}\% }\right)$ as a yellow solid:mp $= {104} - {106}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.89 (d, $J = {7.3}\mathrm{\;{Hz}},2\mathrm{\;H}$ ), ${7.61}\left( {\mathrm{\;d}, J = {7.0}\mathrm{\;{Hz}},4\mathrm{H}}\right)$ , ${7.43}\left( {\mathrm{t}, J = {7.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.35}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 143.9, 141.0, 135.2, 128.7, 127.5, 127.2, 126.4, 83.8, 24.9; IR (film) 2978, 1609, 1398, 1360, 1144, 1092, 766, ${697}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{280}\left( {{\mathrm{M}}^{ + },{67}}\right) ,{265}\left( {21}\right) ,{194}}\right)$ (60), 181 (74), 180 (100), 152 (18).
2-(联苯-4-基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(5f)。${}^{7b}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 500:1，然后 50:1)得到 5f $\left( {{128}\mathrm{{mg}},{91}\% }\right)$ 为黄色固体:熔点 $= {104} - {106}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振氢谱(400 MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 7.89(双峰，$J = {7.3}\mathrm{\;{Hz}},2\mathrm{\;H}$ )，${7.61}\left( {\mathrm{\;d}, J = {7.0}\mathrm{\;{Hz}},4\mathrm{H}}\right)$ ，${7.43}\left( {\mathrm{t}, J = {7.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.35}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100 MHz，CDCl ${}_{3}$ )δ 143.9、141.0、135.2、128.7、127.5、127.2、126.4、83.8、24.9；红外光谱(薄膜)2978、1609、1398、1360、1144、1092、766，${697}{\mathrm{\;{cm}}}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity) }{280}\left( {{\mathrm{M}}^{ + },{67}}\right) ,{265}\left( {21}\right) ,{194}}\right)$ (60)，181(74)，180(100)，152(18)。
4,4,5,5-Tetramethyl-2-(4’-methylbiphenyl-4-yl)-1,3,2-dioxaboro-lane (5g). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1, then 200:1) afforded 5g (117 mg, 80%) as a pale yellow solid:mp = 93-95 ${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.87 (d, $J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.59 (d, $J \; = {7.9}\mathrm{\;{Hz}},2\mathrm{H}),{7.52}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.24}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.39}$ (s, 3H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 143.8, 138.1, 137.3, 135.2, 129.4, 127.0, 126.2, 83.7, 24.8, 21.0; IR (film) 2978, 1609,1399,1360,1145,1092,810 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 294 $\left( {{\mathrm{M}}^{ + },{100}}\right) ,{279}\left( {22}\right) ,{208}\left( {50}\right) ,{195}\left( {72}\right) ,{194}\left( {89}\right) ,{165}$ (22), ${152}\left( {11}\right)$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 295.1867, found 295.1864.
4,4,5,5-四甲基-2-(4’-甲基联苯-4-基)-1,3,2-二氧杂硼烷(5g)。按照典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1，然后200:1)得到5g(117mg，80%)，为浅黄色固体:熔点=93 - 95${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400MHz，CDCl${}_{3}$)$\delta$7.87(d，$J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$)，7.59(d，$J \; = {7.9}\mathrm{\;{Hz}},2\mathrm{H}),{7.52}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.24}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.39}$(s，3H)，1.36(s，12H)；${}^{13}\mathrm{C}$核磁共振(100MHz，CDCl${}_{3}$)δ143.8，138.1，137.3，135.2，129.4，127.0，126.2，83.7，24.8，21.0；红外光谱(薄膜)2978，1609，1399，1360，1145，1092，810${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)294$\left( {{\mathrm{M}}^{ + },{100}}\right) ,{279}\left( {22}\right) ,{208}\left( {50}\right) ,{195}\left( {72}\right) ,{194}\left( {89}\right) ,{165}$(22)，${152}\left( {11}\right)$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$295.1867，实测值为295.1864。
2-(3’-Methoxybiphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxabor-olane (5h). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1, then 100:1) afforded 5h (116mg,75%) as a white solid:mp $= {38} - {40}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDC ${\mathrm{I}}_{3}$ ) $\delta$ 7.88 (d, $J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.60 (d, $J = \; {8.0}\mathrm{\;{Hz}},2\mathrm{H}),{7.35}\left( {\mathrm{t}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.20}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.15}(\mathrm{\;d}$ , $J = {2.1}\mathrm{\;{Hz}},1\mathrm{H}),{6.90}\left( {\mathrm{\;{dd}}, J = {2.4},{8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.86}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.36}(\mathrm{\;s}$ , 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 159.9,143.7,142.5,135.2, 129.7, 126.5, 119.7, 113.0, 112.9, 83.8, 55.3, 24.9; IR (film) 2978, 2360, 1607, 1396, 1360, 1213, 1144, 1092, 733 cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 310 (M ${}^{ + }$ , 100), 295 (21), 224 (47), 211 (72), 210 (89), 209 (19), 180 (13), 167 (17), 141 (13); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{3}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 311.1816, found 311.1822.
2-(3’-甲氧基联苯-4-基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(5h)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1，然后100:1)得到白色固体5h(116mg，75%):熔点$= {38} - {40}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400兆赫，CDC${\mathrm{I}}_{3}$)$\delta$7.88(双峰，$J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$)，7.60(双峰，$J = \; {8.0}\mathrm{\;{Hz}},2\mathrm{H}),{7.35}\left( {\mathrm{t}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.20}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.15}(\mathrm{\;d}$，$J = {2.1}\mathrm{\;{Hz}},1\mathrm{H}),{6.90}\left( {\mathrm{\;{dd}}, J = {2.4},{8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.86}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.36}(\mathrm{\;s}$，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$159.9，143.7，142.5，135.2，129.7，126.5，119.7，113.0，112.9，83.8，55.3，24.9；红外光谱(薄膜)2978，2360，1607，1396，1360，1213，1144，1092，733厘米${}^{-1}$；电子轰击质谱(质荷比，相对强度)310(M${}^{ + }$，100)，295(21)，224(47)，211(72)，210(89)，209(19)，180(13)，167(17)，141(13)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{3}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$311.1816，实测值为311.1822。
3-(4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)- pyridine (5i). ${}^{15}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 50:1, then 5:1) afforded 5i (123 mg, 87%) as a yellow liquid: ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.85 $\left( {\mathrm{s},1\mathrm{H}}\right) ,{8.58}\left( {\mathrm{\;d}, J = {4.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.93}(\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}$ , 2H), 7.89 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 7.9 Hz, 2H), 7.36 (m, 1H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 148.4, 148.1, 140.2, 136.5, 135.4, 134.4, 126.3, 123.5, 83.9, 24.8; IR (film) 2979, 1610, 1360,1144,1093,859,732 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) {281} \; \left( {{\mathrm{M}}^{ + },{75}}\right) ,{266}\left( {38}\right) ,{195}\left( {67}\right) ,{182}\left( {81}\right) ,{181}\left( {100}\right) ,{180}\left( {40}\right) ,{154}$ (16),128 (11); HRMS (ESI) calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 282.1663, found 282.1656.
3-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-吡啶(5i)。${}^{15}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1，然后5:1)得到黄色液体5i(123mg，87%):${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.85 $\left( {\mathrm{s},1\mathrm{H}}\right) ,{8.58}\left( {\mathrm{\;d}, J = {4.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.93}(\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}$ (2H)，7.89(d，J = 8.0Hz，1H)，7.59(d，J = 7.9Hz，2H)，7.36(m，1H)，1.36(s，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl3)δ148.4，148.1，140.2，136.5，135.4，134.4，126.3，123.5，83.9，24.8；红外光谱(薄膜)2979，1610，1360，1144，1093，859，732 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity }}\right) {281} \; \left( {{\mathrm{M}}^{ + },{75}}\right) ,{266}\left( {38}\right) ,{195}\left( {67}\right) ,{182}\left( {81}\right) ,{181}\left( {100}\right) ,{180}\left( {40}\right) ,{154}$ (16)，128(11)；高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{17}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 282.1663，实测值为282.1656。
4,4,5,5-Tetramethyl-2-(4-(thiophen-3-yl)phenyl)-1,3,2-dioxaboro-lane (5j). ${}^{16}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1, then 200:1) afforded 5j (106 mg, 74%) as a pale yellow solid: mp = 90-92 ${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 7.84 (d, $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.60 (d, $J \; = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.50}\left( {\mathrm{{dd}}, J = {1.3},{2.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.41}(\mathrm{{dd}}, J = {1.3},{5.0}\mathrm{\;{Hz}}$ , 1H), ${7.37}\left( {\mathrm{{dd}}, J = {2.8},{5.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 142.2, 138.4, 135.3, 126.3, 126.2, 125.6, 120.9, 83.8, 24.9; IR (film) 2979, 1609, 1359, 1268, 1144, 1093, 860, 738 cm ${}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 286 $\left( {{\mathrm{M}}^{ + },{68}}\right) ,{271}\left( {19}\right) ,{200}\left( {41}\right) ,{187}$ (65), 186 (100), 185 (22), 141 (14).
4,4,5,5-四甲基-2-(4-(噻吩-3-基)苯基)-1,3,2-二氧杂硼烷(5j)。${}^{16}$采用典型方法，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1，然后200:1)得到5j(106mg，74%)，为浅黄色固体:熔点=90-92${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)δ7.84(d，$J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}$)，7.60(d，$J \; = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.50}\left( {\mathrm{{dd}}, J = {1.3},{2.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.41}(\mathrm{{dd}}, J = {1.3},{5.0}\mathrm{\;{Hz}}$，1H)，${7.37}\left( {\mathrm{{dd}}, J = {2.8},{5.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100MHz，CDCl3)δ142.2，138.4，135.3，126.3，126.2，125.6，120.9，83.8，24.9；红外(薄膜)2979，1609，1359，1268，1144，1093，860，738cm${}^{-1}$；电子轰击质谱$(m/z$，相对强度)286$\left( {{\mathrm{M}}^{ + },{68}}\right) ,{271}\left( {19}\right) ,{200}\left( {41}\right) ,{187}$(65)，186(100)，185(22)，141(14)。
Methyl 3’-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl- 4-carboxylate (6a). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 60:1) afforded 6a ( ${140}\mathrm{{mg}},{83}\%$ ) as a yellow solid: $\mathrm{{mp}} = {107} -$ 109 °C; ${}^{1}$ H NMR (400 MHz, CDCl, ${}_{3}$ ) δ 8.10-8.07 (m,3H),7.84 (d, $J \; = {7.4}\mathrm{\;{Hz}},1\mathrm{H}),{7.73} - {7.68}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.47}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.94}(\mathrm{\;s}$ , 3H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 167.0, 145.6, 139.3, 134.5, 133.5, 130.0, 123.0, 128.8, 128.3, 127.1, 83.9, 52.0, 24.9; IR (film) 1724,1609,1358,1276,1140,1105,771,733,708 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) 338 $\left( {{\mathrm{M}}^{ + },{98}),{323}\left( {{34}),{307}\left( {12}\right) ,{252}}\right. }\right.$ (100), 239 (77), 207 (62), 178 (29), 152 (22); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 339.1766, found 339.1762.
3’-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)联苯-4-羧酸甲酯(6a)。按照典型步骤进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后60:1)得到6a(${140}\mathrm{{mg}},{83}\%$)，为黄色固体:$\mathrm{{mp}} = {107} -$熔点109℃；${}^{1}$氢谱(400兆赫兹，氘代氯仿，${}_{3}$)δ8.10 - 8.07(多重峰，3H)，7.84(双峰，$J \; = {7.4}\mathrm{\;{Hz}},1\mathrm{H}),{7.73} - {7.68}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.47}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.94}(\mathrm{\;s}$，3H)，1.36(单峰，12H)；${}^{13}\mathrm{C}$碳谱(100兆赫兹，氘代氯仿${}_{3}$)δ167.0，145.6，139.3，134.5，133.5，130.0，123.0，128.8，128.3，127.1，83.9，52.0，24.9；红外光谱(薄膜)1724,1609,1358,1276,1140,1105,771,733,708${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$(相对强度)338$\left( {{\mathrm{M}}^{ + },{98}),{323}\left( {{34}),{307}\left( {12}\right) ,{252}}\right. }\right.$(100)，239(77)，207(62)，178(29)，152(22)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$339.1766，实测值为339.1762。
3’-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-4-car-bonitrile (6b). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 50:1) afforded 6b (130mg, 85%) as a yellow solid: mp = 88-90°C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.04 (s,1H),7.86 (d, $J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}$ ), ${7.71}\left( {\mathrm{\;s},4\mathrm{H}}\right) ,{7.68} - {7.66}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.48}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.36}(\mathrm{\;s}$ , 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 145.6,138.4,135.0,133.5, 132.4, 129.9, 128.4, 127.7, 118.9, 110.8, 84.0, 24.8; IR (film) 2978, 2228,1727,1607,1359,1143,846,707 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${305}\left( {{\mathrm{M}}^{ + },{62}}\right) ,{290}\left( {48}\right) ,{219}\left( {100}\right) ,{206}\left( {80}\right) ,{205}\left( {82}\right) ,{177}$ (15), 151 (10), 85 (10); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}$ [M + H] ${}^{ + }$ 306.1663, found 306.1665.
3’-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)联苯-4-甲腈(6b)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后50:1)得到黄色固体6b(130mg，产率85%):熔点88 - 90°C；${}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$)δ8.04(s，1H)，7.86(d，$J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}$)，${7.71}\left( {\mathrm{\;s},4\mathrm{H}}\right) ,{7.68} - {7.66}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.48}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.36}(\mathrm{\;s}$，12H)；${}^{13}\mathrm{C}$核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$145.6，138.4，135.0，133.5，132.4，129.9，128.4，127.7，118.9，110.8，84.0，24.8；红外光谱(薄膜)2978，2228，1727，1607，1359，1143，846，707${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)${305}\left( {{\mathrm{M}}^{ + },{62}}\right) ,{290}\left( {48}\right) ,{219}\left( {100}\right) ,{206}\left( {80}\right) ,{205}\left( {82}\right) ,{177}$(15)，151(10)，85(10)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{BNO}}}_{2}$[M + H]${}^{ + }$306.1663，实测值306.1665。
1-(3′-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-3- yl)ethanone (6c). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 50:1) afforded 6c (113 mg, 70%) as a yellow solid:mp = 83-85 ${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.20 (s,1H),8.06 (s,1H),7.92 (d, $J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.83}\left( {\mathrm{t}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.72} - {7.70}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.52}(\mathrm{t}, J \; = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.48}\left( {\mathrm{t}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.66}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right)$ ; ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 198.1,141.7,139.5,137.6,134.2, 133.5, 131.9, 130.0, 128.9, 128.3, 127.1, 127.0, 83.9, 26.8, 24.9; IR (film) 2979,1687,1357,1144,908,732 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 322 $\left( {{\mathrm{M}}^{ + },{100}}\right) ,{307}\left( {48}\right) ,{236}\left( {87}\right) ,{223}\left( {39}\right) ,{207}\left( {61}\right) ,{179}$ (26), ${152}\left( {17}\right)$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{3}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 323.1817, found 323.1816.
1-(3′-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)联苯-3-基)乙酮(6c)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 100:1，然后 50:1)得到 6c(113 mg，70%)，为黄色固体:熔点 = 83 - 85${}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$)δ 8.20(s，1H)，8.06(s，1H)，7.92(d，$J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.83}\left( {\mathrm{t}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.72} - {7.70}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.52}(\mathrm{t}, J \; = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.48}\left( {\mathrm{t}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.66}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right)$；${}^{13}\mathrm{C}$核磁共振(100 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$198.1，141.7，139.5，137.6，134.2，133.5，131.9，130.0，128.9，128.3，127.1，127.0，83.9，26.8，24.9；红外光谱(薄膜)2979，1687，1357，1144，908，732${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)322$\left( {{\mathrm{M}}^{ + },{100}}\right) ,{307}\left( {48}\right) ,{236}\left( {87}\right) ,{223}\left( {39}\right) ,{207}\left( {61}\right) ,{179}$(26)，${152}\left( {17}\right)$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{BO}}}_{3}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$323.1817，实测值为 323.1816。
4,4,5,5-Tetramethyl-2-(3-(thiophene-3-yl)phenyl)-1,3,2-dioxabor-olane (6d). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 500:1, then 250:1) afforded 6d (111 mg, 78%) as a yellow solid: mp = 84-86 ${}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.05 (s,1H), ${7.74}\left( {\mathrm{\;d}, J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${7.69}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.48}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.44} - {7.40}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.38} - {7.35} \; \left( {\mathrm{m},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 142.3},{135.2}$ , 133.5, 132.8, 129.3, 128.2, 126.5, 126.0, 120.4, 83.9, 24.9; IR (film) 2979,1372,1350,1143,855,776,707 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${286}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{271}\left( {20}\right) ,{200}\left( {65}\right) ,{187}\left( {67}\right) ,{186}\left( {93}\right) ,{185}$ (27),141 (13); HRMS (ESI) calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{20}{\mathrm{{BO}}}_{2}\mathrm{\;S}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 287.1275, found 287.1269.
4,4,5,5-四甲基-2-(3-(噻吩-3-基)苯基)-1,3,2-二氧杂硼烷(6d)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1，然后250:1)得到黄色固体6d(111mg，产率78%):熔点84 - 86${}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$) $\delta$ 8.05(s,1H)，${7.74}\left( {\mathrm{\;d}, J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，${7.69}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.48}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.44} - {7.40}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.38} - {7.35} \; \left( {\mathrm{m},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 142.3},{135.2}$，133.5，132.8，129.3，128.2，126.5，126.0，120.4，83.9，24.9；红外光谱(薄膜)2979,1372,1350,1143,855,776,707${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度) ${286}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{271}\left( {20}\right) ,{200}\left( {65}\right) ,{187}\left( {67}\right) ,{186}\left( {93}\right) ,{185}$ (27)，141(13)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{20}{\mathrm{{BO}}}_{2}\mathrm{\;S}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 287.1275，实测值为287.1269。
3-(3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)- pyridine (6e). ${}^{17}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 5:1) afforded 6e (124 mg,88%) as a yellow solid: $\mathrm{{mp}} = {89} - {91}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl, δ 8.86 (s, 1H), 8.58 (s, 1H), 8.03 (s, 1H), ${7.92}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.86}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.67}(\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}$ , $1\mathrm{H}),{7.49}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.36}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 148.1},{137.1},{134.7},{134.6},{134.5},{133.5},{129.9}$ , 128.4, 123.5, 84.0, 24.8; IR (film) 2979, 1357, 1143, 908, 864, 794, 731 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{281}\left( {{\mathrm{M}}^{ + },{96}}\right) ,{266}\left( {48}\right) ,{238}}\right)$ (10), 224 (10), 195 (100), 182 (100), 181 (97), 154 (18), 128 (14).
3-(3-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-吡啶(6e)。${}^{17}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后5:1)得到黄色固体6e(124mg，88%):$\mathrm{{mp}} = {89} - {91}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl，δ8.86(s，1H)，8.58(s，1H)，8.03(s，1H)，${7.92}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.86}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.67}(\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}$ ，$1\mathrm{H}),{7.49}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.36}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 148.1},{137.1},{134.7},{134.6},{134.5},{133.5},{129.9}$ ，128.4，123.5，84.0，24.8；红外光谱(薄膜)2979，1357，1143，908，864，794，731 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{281}\left( {{\mathrm{M}}^{ + },{96}}\right) ,{266}\left( {48}\right) ,{238}}\right)$ (10)，224(10)，195(100)，182(100)，181(97)，154(18)，128(14)。
Typical Procedure for the One-Pot Stille and Suzuki-Miyaura Cross-Coupling Reactions. Under a nitrogen atmosphere, trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyl)- stannane (4b, 0.5 mmol, 184 mg), methyl 4-bromobenzoate (0.5 mmol, 108 mg), Pd(PPh ${ }_{3}{\text{ ) }}_{4}$ (0.025 mmol, 29 mg), and toluene (3 mL) were weighed in a ${25}\mathrm{\;{mL}}$ round-bottom flask. The resulting reaction solution was stirred for ${12}\mathrm{\;h}$ at ${110}{}^{ \circ }\mathrm{C}$ . Then under nitrogen atmosphere, ${\mathrm{K}}_{2}{\mathrm{{CO}}}_{3}\left( {{138}\mathrm{{mg}},1\mathrm{{mmol}}}\right) ,\mathrm{{EtOH}} - {\mathrm{H}}_{2}\mathrm{O}\left( {1\mathrm{{mL}}/1\mathrm{{mL}}}\right)$ , and PhBr ( ${86}\mathrm{{mg}},{0.55}\mathrm{{mmol}}$ ) were directly added in succession. The reaction mixture was stirred for ${12}\mathrm{\;h}$ at ${90}^{ \circ }\mathrm{C}$ . The reaction system was then cooled and filtered through a short silica gel column eluting with dichloromethane. The solution was concentrated under reduced pressure to leave a crude residue, which was purified by silica gel flash column chromatography (petroleum ether/EtOAc = 500:1) to give methyl $m$ -terphenyl-4-carboxylate ${\left( 7a\right) }^{18}$ in 58% isolated yield (84 mg) as a white solid:mp $= {115} - {117}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.12 $\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.82}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.70}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.63} \; \left( {\mathrm{d}, J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.60}\left( {\mathrm{t}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.52}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${7.46}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.37}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.93}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 166.9, 145.5, 142.0, 140.9, 140.5, 130.1, 129.3, 129.0, 128.8, 127.5, 127.2, 127.1, 127.1, 126.9, 126.2, 52.1; IR (film) 2989, 1719, 1282, 1109, 1066, 756, 701 cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 288 (M ${}^{ + }$ , 100), 277 (6), 257 (73), 228 (28), 207 (25), 129 (14), 114 (10).
一锅法施蒂勒反应和铃木-宫浦交叉偶联反应的典型步骤。在氮气气氛下，将三甲基(3-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)锡烷(4b，0.5 mmol，184 mg)、4-溴苯甲酸甲酯(0.5 mmol，108 mg)、Pd(PPh${ }_{3}{\text{ ) }}_{4}$(0.025 mmol，29 mg)和甲苯(3 mL)加入到一个${25}\mathrm{\;{mL}}$圆底烧瓶中。将所得反应溶液在${110}{}^{ \circ }\mathrm{C}$搅拌${12}\mathrm{\;h}$。然后在氮气气氛下，依次直接加入${\mathrm{K}}_{2}{\mathrm{{CO}}}_{3}\left( {{138}\mathrm{{mg}},1\mathrm{{mmol}}}\right) ,\mathrm{{EtOH}} - {\mathrm{H}}_{2}\mathrm{O}\left( {1\mathrm{{mL}}/1\mathrm{{mL}}}\right)$和PhBr(${86}\mathrm{{mg}},{0.55}\mathrm{{mmol}}$)。反应混合物在${90}^{ \circ }\mathrm{C}$搅拌${12}\mathrm{\;h}$。然后将反应体系冷却，通过用二氯甲烷洗脱的短硅胶柱过滤。溶液在减压下浓缩，得到粗残余物，通过硅胶快速柱色谱法(石油醚/乙酸乙酯=500:1)纯化，得到$m$-三联苯-4-羧酸甲酯${\left( 7a\right) }^{18}$，分离产率为58%(8 mg)，为白色固体:熔点$= {115} - {117}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$；核磁共振氢谱(400 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$8.12$\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.82}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.70}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.63} \; \left( {\mathrm{d}, J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.60}\left( {\mathrm{t}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.52}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，${7.46}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.37}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.93}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$；核磁共振碳谱(100 MHz，CDCl${}_{3}$)δ166.9、145.5、142.0、140.9、140.5、130.1、129.3、129.0、128.8、127.5、127.2、127.1、127.1、126.9、126.2、52.1；红外光谱(薄膜)2989、1719、1282；1109、1066、756、701 cm${}^{-1}$；电子轰击质谱(m/z，相对强度)288(M${}^{ + }$，100)、277(6)、257(73)、228(28)、207(25)、129(14)、114(10)。
3-([1,1’-Biphenyl]-3-yl)pyridine (7b). ${}^{19}$ The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 15:1) afforded 7b (76 mg, 66%) as a pale yellow liquid: ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.91 (d, $J = {1.9}\mathrm{\;{Hz}},1\mathrm{H}$ ), ${8.62}\left( {\mathrm{{dd}}, J = {1.3},{4.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.93}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.78}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.65} - {7.63} \; \left( {\mathrm{m},3\mathrm{H}}\right) ,{7.56} - {7.54}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.47}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.40} - {7.36}(\mathrm{\;m}$ , 2H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.5,148.3,142.2,140.8, 138.4, 136.7, 134.6, 129.5, 128.9, 127.6, 127.3, 127.0, 126.1, 126.1, 123.6; IR (film) 2926, 1726, 1599, 1469, 1286, 1075, 1024, 907, 757 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity $){231}\left( {{\mathrm{M}}^{ + },{100}),{230}\left( {24}\right) ,{202}}\right.$ (12), 152 (10).
3-([1,1’-联苯]-3-基)吡啶(7b)。${}^{19}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后15:1)得到7b(76毫克，66%)，为浅黄色液体:${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.91(双峰，$J = {1.9}\mathrm{\;{Hz}},1\mathrm{H}$ )，${8.62}\left( {\mathrm{{dd}}, J = {1.3},{4.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.93}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.78}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.65} - {7.63} \; \left( {\mathrm{m},3\mathrm{H}}\right) ,{7.56} - {7.54}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.47}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.40} - {7.36}(\mathrm{\;m}$ ，2H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.5、148.3、142.2、140.8、138.4、136.7、134.6、129.5、128.9、127.6、127.3、127.0、126.1、126.1、123.6；红外光谱(薄膜)2926、1726、1599、1469、1286、1075、1024、907、757 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$\left( {m/z}\right.$ ，相对强度$){231}\left( {{\mathrm{M}}^{ + },{100}),{230}\left( {24}\right) ,{202}}\right.$ (12)，152(10)。
1-([1,1’:3’,1"-Terphenyl]-3-yl)ethan-1-one (7c). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1, then 100:1) afforded 7c (82 mg, 60%) as a pale yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.22 (s,1H), ${7.94}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.84} - {7.81}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.64}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.59}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.54}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.46}(\mathrm{t}, J = {7.6}\mathrm{\;{Hz}}$ , $2\mathrm{H}),{7.37}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.65}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $({100}\mathrm{{MHz}}$ , CDCl ${}_{3}$ ) $\delta$ 198.0,142.0,141.7,140.9,140.7,137.7,131.8,129.3,129.1, 128.8, 127.5, 127.3, 127.2, 127.0, 126.6, 126.1, 26.7; IR (film) 1684, 1598,1356,1268,1226,908,758 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) ${272}\left( {{\mathrm{M}}^{ + },{92}}\right) ,{257}\left( {100}\right) ,{229}\left( {38}\right) ,{228}\left( {37}\right) ,{202}\left( {15}\right) ,{152}$ (10),113 (10); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{17}\mathrm{O}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{273.1274}$ , found 273.1268.
1-([1,1’:3’,1"-三联苯]-3-基)乙-1-酮(7c)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1，然后100:1)得到7c(82毫克，60%)，为浅黄色油状物:${}^{1}\mathrm{H}$核磁共振(400兆赫，氘代氯仿${}_{3}$)δ8.22(单峰，1H)，${7.94}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.84} - {7.81}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.64}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}}\right)$，${7.59}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.54}\left( {\mathrm{t}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.46}(\mathrm{t}, J = {7.6}\mathrm{\;{Hz}}$，$2\mathrm{H}),{7.37}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.65}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$({100}\mathrm{{MHz}}$，氘代氯仿${}_{3}$)$\delta$198.0,142.0,141.7,140.9,140.7,137.7,131.8,129.3,129.1,128.8,127.5,127.3,127.2,127.0,126.6,126.1,26.7；红外光谱(薄膜)1684,1598,1356,1268,1226,908,758${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度)${272}\left( {{\mathrm{M}}^{ + },{92}}\right) ,{257}\left( {100}\right) ,{229}\left( {38}\right) ,{228}\left( {37}\right) ,{202}\left( {15}\right) ,{152}$(10)，113(10)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{17}\mathrm{O}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{273.1274}$，实测值为273.1268。
4″-Methoxy[1,1′:3′,1″-terphenyl]-3-carbonitrile (7d). The typical procedure was followed, and flash chromatography (silica gel, petroleum ether/EtOAc = 250:1) afforded 7d (93 mg, 65%) as a yellow oil: ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.89 (s,1H),7.84 (d, $J = \; {7.9}\mathrm{\;{Hz}},1\mathrm{H}),{7.70}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.63}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.59} - {7.57}(\mathrm{\;m}$ 2H), 7.56-7.54 (m, 2H), 7.52-7.46 (m, 2H), 7.00 (d, J = 8.6 Hz, 2H), 3.85 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl, δ 159.4, 142.4, 141.8, 139.3, 133.1, 131.5, 130.7, 129.6, 129.5, 128.2, 126.7, 125.5, 125.3, 118.8, 114.3, 112.9, 55.3; IR (film) 2230, 1610, 1517, 1291, 1246,1181,908,778,732 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 285 $\left( {{\mathrm{M}}^{ + },{100}}\right) ,{270}\left( {21}\right) ,{242}\left( {22}\right) ,{240}\left( {13}\right) ,{227}\left( {10}\right) ,{214}\left( 5\right) ,{143}\left( 6\right) ;$ HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{16}\mathrm{{NO}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{286.1226}$ , found 286.1224.
4″-甲氧基[1,1′:3′,1″-三联苯]-3-甲腈(7d)。按照典型程序操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=250:1)得到7d(93mg，65%)，为黄色油状物:${}^{1}\mathrm{H}$核磁共振(400MHz，CDCl${}_{3}$)$\delta$7.89(s，1H)，7.84(d，$J = \; {7.9}\mathrm{\;{Hz}},1\mathrm{H}),{7.70}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.63}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.59} - {7.57}(\mathrm{\;m}$2H)，7.56 - 7.54(m，2H)，7.52 - 7.46(m，2H)，7.00(d，J = 8.6Hz，2H)，3.85(s，3H)；${}^{13}\mathrm{C}$核磁共振(100MHz，CDCl，δ159.4，142.4，141.8，139.3，133.1，131.5，130.7，129.6，129.5，128.2，126.7，125.5，125.3，118.8，114.3，112.9，55.3；红外光谱(薄膜)2230，1610，1517，1291，1246，1181，908，778，732${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)285$\left( {{\mathrm{M}}^{ + },{100}}\right) ,{270}\left( {21}\right) ,{242}\left( {22}\right) ,{240}\left( {13}\right) ,{227}\left( {10}\right) ,{214}\left( 5\right) ,{143}\left( 6\right) ;$高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{16}\mathrm{{NO}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{286.1226}$，实测值286.1224。
4-Methoxy-4"-nitro-1,1’:3’,1"-terphenyl (7e). The typical procedure was followed, and flash chromatography (silica gel, petroleum ether/EtOAc = 250:1, then 100:1) afforded 7e (83 mg, 55%) as a pale yellow solid: $\mathrm{{mp}} = {128} - {130}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.29 $\left( {\mathrm{d}, J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.77} - {7.75}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.56} - {7.57}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.57}(\mathrm{\;d}, J \; = {8.8}\mathrm{\;{Hz}},2\mathrm{H}),{7.53} - {7.52}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.00}\left( {\mathrm{\;d}, J = {8.7}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.86}(\mathrm{\;s}$ , 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 159.5,147.6,147.1,141.8, 139.3, 133.0, 129.5, 128.2, 127.9, 127.2, 125.8, 125.6, 124.1, 114.3, 55.3; IR (film) 1597, 1519, 1347, 1256, 1018, 906, 797, 730 cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 305 (M }{}^{ + }\text{ ,100),290 (14),275 (7),262 }}\right)$ (7),215 (21),189 (7),95 (5); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{16}{\mathrm{{NO}}}_{3}$ [M + H]* 306.1125, found 306.1122.
4-甲氧基-4’’-硝基-1,1’:3’,1’’-三联苯(7e)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 250:1，然后 100:1)得到 7e(83 毫克，55%)，为淡黄色固体:$\mathrm{{mp}} = {128} - {130}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400 兆赫，CDCl ${}_{3}$ )δ 8.29 $\left( {\mathrm{d}, J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.77} - {7.75}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.56} - {7.57}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.57}(\mathrm{\;d}, J \; = {8.8}\mathrm{\;{Hz}},2\mathrm{H}),{7.53} - {7.52}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.00}\left( {\mathrm{\;d}, J = {8.7}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.86}(\mathrm{\;s}$ ，3H)；${}^{13}\mathrm{C}$核磁共振(100 兆赫，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 159.5,147.6,147.1,141.8, 139.3, 133.0, 129.5, 128.2, 127.9, 127.2, 125.8, 125.6, 124.1, 114.3, 55.3；红外光谱(薄膜)1597, 1519, 1347, 1256, 1018, 906, 797, 730 厘米 ${}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity) 305 (M }{}^{ + }\text{ ,100),290 (14),275 (7),262 }}\right)$ (7),215(21),189(7),95(5)；高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{19}{\mathrm{H}}_{16}{\mathrm{{NO}}}_{3}$ [M + H]* 306.1125，实测值为 306.1122。
Methyl [1,1’:4’,1"-Terphenyl]-4-carboxylate (7f). The typical procedure was followed, and flash chromatography (petroleum ether, then petroleum ether-EtOAc = 20:1) afforded 7f (91 mg, 63%) as a yellow solid: $\mathrm{{mp}} = {188} - {190}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.13 $\left( {d, J = {8.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.73} - {7.71}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.66} - {7.64}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.47}(\mathrm{t}, J \; = {7.6}\mathrm{\;{Hz}},2\mathrm{H}),{7.38}\left( {\mathrm{t},\mathrm{J} = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.95}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {100}\right)$ MHz, CDCl3) δ 167.0, 145.1, 141.0, 140.4, 138.8, 132.3, 130.9, 130.1, 128.8, 127.6, 127.5, 127.0, 126.9, 52.1; IR (film) 2927, 2855, 1720, ${1282},{1114},{907},{758}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${288}\left( {\mathrm{M}}^{ + }\right.$ , 100), 257 (62), 228 (33), 202 (15), 152 (14); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{17}{\mathrm{O}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{289.1223}$ , found 289.1220.
甲基 [1,1’:4’,1"-三联苯]-4-羧酸酯(7f)。按照典型程序操作，通过快速柱色谱法(石油醚，然后石油醚 - 乙酸乙酯 = 20:1)得到黄色固体7f(91 mg，63%):$\mathrm{{mp}} = {188} - {190}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)δ 8.13 $\left( {d, J = {8.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.73} - {7.71}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.66} - {7.64}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.47}(\mathrm{t}, J \; = {7.6}\mathrm{\;{Hz}},2\mathrm{H}),{7.38}\left( {\mathrm{t},\mathrm{J} = {7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.95}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {100}\right)$兆赫，CDCl3)δ 167.0，145.1，141.0，140.4，138.8，132.3，130.9，130.1，128.8，127.6，127.5，127.0，126.9，52.1；红外光谱(薄膜)2927，2855，1720，${1282},{1114},{907},{758}{\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)${288}\left( {\mathrm{M}}^{ + }\right.$，100)，257(62)，228(33)，202(15)，152(14)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{17}{\mathrm{O}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{289.1223}$，实测值289.1220。
1-(4″-tert-Butyl[1,1′:4′,1″-terphenyl]-3-yl)ethan-1-one (7g). The typical procedure was followed, and flash column chromatography (petroleum ether, then petroleum ether-EtOAc = 100:1) afforded 7g (95 mg, 58%) as a white solid:mp = 136-138 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.22 (s,1H),7.92 (d, $J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.82}(\mathrm{\;d}, J = {7.8} \; \mathrm{{Hz}},1\mathrm{H}),{7.68}\left( {\mathrm{\;s},4\mathrm{H}}\right) ,{7.58}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.53}(\mathrm{t}, J = {7.7}\mathrm{\;{Hz}}$ , 1H), ${7.48}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},2\mathrm{\;H}}\right) ,{2.65}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 197.9,150.5,141.2,140.5,138.6,137.6,137.5, 131.5, 129.0, 127.4, 127.1, 126.7, 126.6, 125.7, 34.5, 31.3, 26.7; IR (film) 2964,1679,1599,1356,1238,908,731 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 328 (M ${}^{ + }$ , 55), 314 (27), 313 (100), 285 (13), 226 (10),149 (10); HRMS (ESI) calcd for ${\mathrm{C}}_{24}{\mathrm{H}}_{25}\mathrm{O}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 329.1900, found 329.1906.
1-(4″-叔丁基[1,1′:4′,1″-三联苯]-3-基)乙-1-酮(7g)。按照典型程序进行操作，通过快速柱色谱法(石油醚，然后石油醚-乙酸乙酯=100:1)得到7g(95mg，58%)白色固体:熔点=136-138°C；${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$8.22(单峰，1H)，7.92(双峰，$J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.82}(\mathrm{\;d}, J = {7.8} \; \mathrm{{Hz}},1\mathrm{H}),{7.68}\left( {\mathrm{\;s},4\mathrm{H}}\right) ,{7.58}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.53}(\mathrm{t}, J = {7.7}\mathrm{\;{Hz}}$，1H)，${7.48}\left( {\mathrm{\;d}, J = {8.4}\mathrm{\;{Hz}},2\mathrm{\;H}}\right) ,{2.65}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$197.9，150.5，141.2，140.5，138.6，137.6，137.5，131.5，129.0，127.4，127.1，126.7，126.6，125.7，34.5，31.3，26.7；红外光谱(薄膜)2964，1679，1599，1356,1238,908,731${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)328(M${}^{ + }$，55)，314(27)，313(100)，285(13)，226(10)，149(10)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{24}{\mathrm{H}}_{25}\mathrm{O}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$329.1900，实测值为329.1906。
3-(4’-tert-Butyl[1,1’-biphenyl]-4-yl)pyridine (7h). The typical procedure was followed, and flash column chromatography (petroleum ether-ethyl acetate =100:1, then petroleum ether-EtOAc = 20:1) afforded $7\mathbf{h}\left( {{103}\mathrm{{mg}},{72}\% }\right)$ as a pale yellow solid: $\mathrm{{mp}} = {144} - {146} \; {}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) ${\delta 8.91}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.59}(\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}$ , 1H), 7.91 (d, J = 7.9 Hz, 1H), 7.70 (d, J = 8.2 Hz, 2H), 7.64 (d, J = 8.2 $\mathrm{{Hz}},2\mathrm{H}),{7.58}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.49}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.38} - {7.35} \; \left( {\mathrm{m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.6},{148.2}$ , 147.9, 140.8, 137.3, 136.2, 134.2, 127.5, 127.3, 126.6, 125.7, 123.5, 34.5, 31.3; IR (film) 2956, 1728, 1475, 1391, 1277, 1238, 908, 731 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity) ${287}\left( {{\mathrm{M}}^{ + },{52}}\right) ,{272}\left( {100}\right) ,{244}$ (17),231 (10),122 (15); HRMS (ESI) calcd for ${\mathrm{C}}_{21}{\mathrm{H}}_{22}\mathrm{\;N}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 288.1747, found 288.1740.
3-(4’-叔丁基[1,1’-联苯]-4-基)吡啶(7h)。按照典型程序进行操作，通过快速柱色谱法(石油醚 - 乙酸乙酯 = 100:1，然后石油醚 - 乙酸乙酯 = 20:1)得到$7\mathbf{h}\left( {{103}\mathrm{{mg}},{72}\% }\right)$，为浅黄色固体:$\mathrm{{mp}} = {144} - {146} \; {}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) ${\delta 8.91}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.59}(\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}$ ，1H)，7.91(双峰，J = 7.9赫兹，1H)，7.70(双峰，J = 8.2赫兹，2H)，7.64(双峰，J = 8.2 $\mathrm{{Hz}},2\mathrm{H}),{7.58}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.49}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.38} - {7.35} \; \left( {\mathrm{m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},9\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.6},{148.2}$ ，147.9，140.8，137.3，136.2，134.2，127.5，127.3，126.6，125.7，123.5，34.5，31.3；红外(薄膜)2956，1728，1475，1391，1277，1238，908，731 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(质荷比，相对强度) ${287}\left( {{\mathrm{M}}^{ + },{52}}\right) ,{272}\left( {100}\right) ,{244}$ (17)，231(10)，122(15)；高分辨质谱(电喷雾电离)计算得到${\mathrm{C}}_{21}{\mathrm{H}}_{22}\mathrm{\;N}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 288.1747，实测值288.1740。
[1,1’:4’,1"-Terphenyl]-3-carbaldehyde (7i). The typical procedure was followed, and flash column chromatography (silica gel, petroleum ether, then petroleum ether/EtOAc = 100:1) afforded 7i (65 mg, 50%) as a white solid: mp = ${148} - {149}{}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 10.09 (s,1H),8.14 (s,1H),7.90-7.85 (m,2H),7.70 (s, 4H), 7.65-7.59 (m, 3H), 7.46 (t, J = 7.6 Hz, 2H), 7.37 (t, J = 7.3 Hz, 1H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 192.2,141.6,140.9,140.4, 138.5, 137.0, 132.8, 129.5, 128.8, 128.7, 128.0, 127.7, 127.5, 127.5, 127.0; IR (film) 2927,1703,1585,1481,1379,1183,908 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{258}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{257}\left( {16}\right) ,{229}\left( {22}\right) ,{228}({27}}\right)$ , ${152}\left( {11}\right) ,{113}\left( {10}\right) ;$ HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{15}\mathrm{O}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 259.1117, found 259.1118.
[1,1’:4’,1"-三联苯]-3-甲醛(7i)。按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚，然后石油醚/乙酸乙酯=100:1)得到白色固体7i(65毫克，50%):熔点=${148} - {149}{}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$10.09(单峰，1H)，8.14(单峰，1H)，7.90 - 7.85(多重峰，2H)，7.70(单峰，4H)，7.65 - 7.59(多重峰，3H)，7.46(三重峰，J = 7.6赫兹，2H)，7.37(三重峰，J = 7.3赫兹，1H)；${}^{13}\mathrm{C}$核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$192.2，141.6，140.9，140.4，138.5，137.0，132.8，129.5，128.8，128.7，128.0，127.7，127.5，127.5，127.0；红外光谱(薄膜)2927，1703，1585，1481，1379，1183，908${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{258}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{257}\left( {16}\right) ,{229}\left( {22}\right) ,{228}({27}}\right)$，${152}\left( {11}\right) ,{113}\left( {10}\right) ;$高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{15}\mathrm{O}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$259.1117，实测值为259.1118。
[1,1’:4’,1"-Terphenyl]-4-carbonitrile (7j): ${}^{20}$ The typical procedure was followed, and flash chromatography (silica gel, petroleum ether/ EtOAc = 100:1, then 20:1) afforded 7j (73 mg, 57%) as a white solid: mp $= {188} - {190}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.71-7.62 (m, ${10}\mathrm{H}),{7.46}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.38}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 145.1},{141.5},{140.1},{137.9},{132.6},{128.9},{127.7}$ , 127.7, 127.5, 127.5, 127.0, 118.9, 110.9; IR (film) 2925, 2231, 1603, ${1483},{1435},{1104},{907}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${255}\left( {\mathrm{M}}^{ + }\right.$ , 100), 254 (12), 253 (11), 152 (10), 113 (8).
[1,1’:4’,1"-三联苯]-4-甲腈(7j):${}^{20}$ 按照典型程序进行操作，通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后20:1)得到白色固体7j(73mg，产率57%):熔点 $= {188} - {190}{}^{ \circ }\mathrm{C};{}^{1}\mathrm{H}$ 核磁共振(400MHz，CDCl ${}_{3}$ ) $\delta$ 7.71 - 7.62(多重峰，${10}\mathrm{H}),{7.46}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.38}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 145.1},{141.5},{140.1},{137.9},{132.6},{128.9},{127.7}$ ，127.7，127.5，127.5，127.0，118.9，110.9；红外光谱(薄膜)2925，2231，1603，${1483},{1435},{1104},{907}{\mathrm{\;{cm}}}^{-1}$ ；电子轰击质谱$(m/z$ ，相对强度)${255}\left( {\mathrm{M}}^{ + }\right.$ ，100)，254(12)，253(11)，152(10)，113(8)。
A ASSOCIATED CONTENT
A 相关内容
⑤ Supporting Information
⑤ 支持信息
Copies of ${}^{1}\mathrm{H}$ and ${}^{13}\mathrm{C}$ spectra for all products. This material is available free of charge via the Internet at http://pubs.acs.org.
所有产品的${}^{1}\mathrm{H}$和${}^{13}\mathrm{C}$光谱副本。此材料可通过互联网免费获取，网址为http://pubs.acs.org。
A AUTHOR INFORMATION
A作者信息
Corresponding Author
通讯作者
Notes
注释
The authors declare no competing financial interest.
作者声明不存在利益冲突。
ACKNOWLEDGMENTS
致谢
This project was supported by the National Basic Research Program of China (973 Program, 2012CB821600) and the National Natural Science Foundation of China (Grant Nos. 21272010 and 21332002).
本项目得到了中国国家基础研究计划(973计划，2012CB821600)和中国国家自然科学基金(批准号:21272010和21332002)的支持。
REFERENCES
参考文献
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