Synthesis of Pinacol Arylboronates from Aromatic Amines: A Metal-Free Transformation

英文原文与中文译文逐段对照 · English original with Chinese translation

Di Qiu, Liang Jin, Zhitong Zheng, He Meng, Fanyang Mo,* Xi Wang, Yan Zhang, and Jianbo Wang*

邱迪，金亮，郑志通，何萌，莫凡洋*，王曦，张岩，王剑波*

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

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

S Supporting Information

支持信息

ABSTRACT: A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.

摘要:开发了一种以芳胺衍生物为底物、基于桑德迈尔型转化的无金属硼化过程。通过优化反应条件，这种新型转化可成功应用于多种芳香胺，以中等至良好的产率得到硼化产物。通过这种无金属转化可以轻松获得各种其他方法难以得到的功能化芳基硼酸酯。此外，该转化之后可进行铃木 - 宫浦交叉偶联而无需纯化硼化产物，这增强了该方法的实用性。提出了一种可能涉及自由基物种的反应机理。

INTRODUCTION

引言

Arylboronic acids and arylboronates have shown great importance due to their widespread applications in organic synthesis and other fields. ${}^{1,2}$ In particular, functionalized arylboronic acids and arylboronates are highly valuable because consecutive cross-coupling is possible from these compounds, which can rapidly construct the complex structure of target molecules. ${}^{3}$ Consequently, the syntheses of various functionalized arylboronic compounds have attracted significant attentions in recent years.

芳基硼酸和芳基硼酸酯由于在有机合成及其他领域的广泛应用而显得极为重要。${}^{1,2}$ 特别是，官能团化的芳基硼酸和芳基硼酸酯具有很高的价值，因为这些化合物可以进行连续的交叉偶联反应，从而能够快速构建目标分子的复杂结构。${}^{3}$ 因此，近年来各种官能团化芳基硼酸化合物的合成引起了广泛关注。

The reaction of aryl Grignard reagents or aryllithium species with trialkyl boronates remains the most general synthetic method to prepare aromatic boronic compounds (Scheme 1, path $a$ ). ${}^{4}$ In 1995, Miyaura et al. developed the palladium-catalyzed borylation of arylhalides using bis(pinacolato)diboron as the boron source. ${}^{5}$ Subsequently, Masuda et al. reported the palladium-catalyzed borylation from arylhalides using pinacol-borane. ${}^{6}$ The groups of Ma and Marder then reported the copper-catalyzed borylation reaction (Scheme 1, path $b$ ). ${}^{7}$ In the past decade, direct borylation via aromatic $\mathrm{C} - \mathrm{H}$ bond activation has been extensively explored in the groups of Smith III, Miyaura, Hartwig, Marder, and others (Scheme 1, path $c$ ). ${}^{8}$ Recently, Lewis acid catalyzed electrophilic borylation of electron-rich arenes has been explored (Scheme 1, path d). ${}^{9,{10}}$ These borylation methods have the advantage of being transition-metal-free processes and thus avoiding heavy metal contamination in the final products.

芳基格氏试剂或芳基锂试剂与硼酸三烷基酯的反应仍然是制备芳基硼酸化合物最常用的合成方法(方案1，路径$a$)。${}^{4}$ 1995年，宫浦等人开发了以双(频哪醇)二硼为硼源，钯催化芳基卤化物的硼化反应。${}^{5}$ 随后，增田等人报道了以频哪醇硼烷为原料，钯催化芳基卤化物的硼化反应。${}^{6}$ 马和马德的研究小组随后报道了铜催化的硼化反应(方案1，路径$b$)。${}^{7}$ 在过去十年中，史密斯三世、宫浦、哈特维希、马德等研究小组对通过芳族$\mathrm{C} - \mathrm{H}$ 键活化进行直接硼化反应进行了广泛探索(方案1，路径$c$)。${}^{8}$ 最近，人们探索了路易斯酸催化的富电子芳烃的亲电硼化反应(方案1，路径d)。${}^{9,{10}}$ 这些硼化方法的优点是无过渡金属参与，从而避免了最终产物中的重金属污染。

Scheme 1. Different Routes to Arylboronic Acids or Arylboronates

方案1. 芳基硼酸或芳基硼酸酯的不同合成路线

We have recently communicated an entirely different approach toward arylboronates synthesis by direct conversion of the amino group of aniline derivatives to the boronate group (Scheme 1, path $e$ ). ${}^{11}$ This transformation is under Sandmeyer-type reaction conditions by using tert-butyl nitrite ( $t$ -BuONO) as diazotization agent. ${}^{{12},{13}}$ This borylation method has the following features: (1) the reaction is under metal-free conditions, (2) arylamines are cheap and abundant starting materials, (3) the borylation tolerates various functional groups, and (4) the reaction is under very mild conditions. As a result, this novel borylation will not only find wide application in organic synthesis but also shed light on the unique reactivity of aryldiazonium ion and diboron compounds. ${}^{14}$

我们最近报道了一种完全不同的芳基硼酸酯合成方法，即将苯胺衍生物的氨基直接转化为硼酸酯基(方案1，路径$e$)。${}^{11}$ 该转化反应是在桑德迈尔型反应条件下，使用亚硝酸叔丁酯($t$ -BuONO)作为重氮化试剂。${}^{{12},{13}}$ 这种硼化方法具有以下特点:(1)反应在无金属条件下进行；(2)芳胺是廉价且丰富的起始原料；(3)硼化反应能耐受各种官能团；(4)反应条件非常温和。因此，这种新型硼化反应不仅将在有机合成中得到广泛应用，还将为芳基重氮离子和二硼化合物的独特反应性提供新的见解。${}^{14}$

In this article, we report the further optimization of the reaction conditions and the expansion of the substrate scope to various aniline derivatives. Compared to the results reported in the preliminary communication, the newly optimized reaction conditions offered improved yields and have wider substrate scope. Moreover, this borylation has also been extended to heterocyclic amines, although with limited success.

在本文中，我们报道了反应条件的进一步优化以及底物范围扩展到各种苯胺衍生物。与初步报道的结果相比，新优化的反应条件提高了产率并扩大了底物范围。此外，这种硼化反应也已扩展到杂环胺，尽管成功有限。

RESULTS AND DISCUSSION

结果与讨论

To further optimize the reaction that was reported in our preliminary communication, ${}^{11}$ we have chosen 2-amino-benzonitrile as the substrate, with which only a low yield of

为了进一步优化我们初步通讯中报道的反应，${}^{11}$ 我们选择了2-氨基苯甲腈作为底物，与之反应时产率较低

Special Issue: Howard Zimmerman Memorial Issue

特刊:霍华德·齐默尔曼纪念特刊

Received: September 2, 2012

收到日期:2012年9月2日

22% was obtained under the previous reaction conditions [ $t$ - BuONO, benzoyl peroxide (BPO, 2 mol %), MeCN, rt] (Table 1, entry 1). Thus, a number of experiments were conducted to improve the yield, and these experiments provide further insight into the factors that affect this transformation. First, it was observed that the reaction is significantly affected by temperature (entries 2-4). The yield of 4aa could be improved when the reaction was carried at elevated temperature. At 80 ${}^{ \circ }\mathrm{C}$ ,4aa could be obtained in 77% GC yield and 66% isolated yield. Addition of radical initiator BPO slightly affects the reaction at this temperature (entries 5-7). Use of other solvents, such as toluene, DCE, and dioxane, proved to be ineffective. Finally, alkyl nitrites 2b and 2c were found to be compatible with this reaction, albeit less efficient than 2a (entries 11,12).

在之前的反应条件下[$t$叔丁基亚硝酸酯、过氧化苯甲酰(BPO，2 mol%)、乙腈、室温]，得到了22%的产率(表1，第1项)。因此，进行了许多实验以提高产率，这些实验进一步深入了解了影响该转化的因素。首先，观察到反应受温度的影响很大(第2 - 4项)。当反应在升高的温度下进行时，4aa的产率可以提高。在80${}^{ \circ }\mathrm{C}$时，4aa的气相色谱产率为77%，分离产率为66%。在该温度下，加入自由基引发剂BPO对反应的影响较小(第5 - 7项)。使用其他溶剂，如甲苯、二氯乙烷和二氧六环，证明是无效的。最后，发现亚硝酸烷基酯2b和2c与该反应兼容，尽管效率不如亚硝酸烷基酯2a(第11、12项)。

Table 1. Optimization of Reaction Conditions for 2- ${\text{ Aminobenzonitrile }}^{a}$

表1. 2-${\text{ Aminobenzonitrile }}^{a}$反应条件的优化

“Reaction conditions: arylamine (1 mmol), ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ (1.1 mmol), RONO (1.5 mmol),1 h. ${}^{b}\mathrm{{GC}}$ yield measured with $\mathrm{{GC}} - \mathrm{{MS}}$ , mesitylene was used as internal standard. ${}^{c}$ See ref 11. ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ : bis(pinacolato)diboron. Bpin: 4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl.

“反应条件:芳胺(1 mmol)，${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$(1.1 mmol)，亚硝酸酯(1.5 mmol)，1小时。${}^{b}\mathrm{{GC}}$产率用$\mathrm{{GC}} - \mathrm{{MS}}$测定，均三甲苯用作内标。${}^{c}$见参考文献11。${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$:双(频哪醇合)二硼。Bpin:4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基。

The optimization experiments demonstrate that by simply raising reaction temperature, the yield of the borylation product could be markedly improved. With this in hand, the aniline substrates that afforded the low yields of the corresponding borylation products under the previous conditions were examined, and the yields were compared (Scheme 2). The results show that in general the yields are improved when the reactions are carried out at high temperature, especially for those with halogen substituents (4ab, 4ac, 4af, 4ah).

优化实验表明，通过简单提高反应温度，硼化产物的产率可以显著提高。基于此，我们研究了在之前条件下相应硼化产物产率较低的苯胺底物，并比较了产率(方案2)。结果表明，一般来说，当反应在高温下进行时，产率会提高，特别是对于那些带有卤素取代基的底物(4ab、4ac, 4af, 4ah)。

Encouraged by the results, we proceeded to apply this metal-free borylation to a series of new substrates. First, parasubstituted aniline derivatives were investigated (Scheme 3). Moderate to good yields were obtained for most of the parasubstituted aniline substrates. The borylation showed good tolerance to various functional groups, including methylthio (4ba), hydroxyl (4bb), formyl (4bc), carboxyl (4bd), sulfonyl (4be), azo (4bf), amino (4bh), iodo (4bk), and alkynyl (4bj) groups. In the cases of 4bc, 4bg, and 4bl, the low yields are due to their low stability on column chromatography or TLC. When 4-aminostryne was employed as the substrate, the corresponding boronate 4bg was isolated in very low yield. In this case, a large quantity of precipitate was observed. We speculate that polymerization occurs in this reaction, which may be initiated by a radical intermediate (vide infra). Interestingly, with $p$ -aminoaniline as the substrate, selective mono- or diborylation could be realized by simply controlling the amount of $t$ -BuONO and ${\mathrm{B}}_{2}{\text{ pin }}_{2}$ used in the reaction (4bh and 4bi).

受这些结果的鼓舞，我们继续将这种无金属硼化反应应用于一系列新底物。首先，研究了对取代苯胺衍生物(方案3)。大多数对取代苯胺底物获得了中等至良好的产率。硼化反应对各种官能团具有良好的耐受性，包括甲硫基(4ba)、羟基(4bb)、甲酰基(4bc)、羧基(4bd)、磺酰基(4be)、偶氮基(4bf)、氨基(4bh)、碘代(4bk)和炔基(4bj)基团。在4bc、4bg和4bl的情况下，产率较低是由于它们在柱色谱或薄层色谱上的稳定性较差。当使用4-氨基苯乙炔作为底物时，相应的硼酸酯4bg的分离产率非常低。在这种情况下，观察到大量沉淀。我们推测该反应中发生了聚合反应，这可能由自由基中间体引发(见下文)。有趣的是，以$p$-氨基苯胺为底物，通过简单控制反应中使用的$t$-叔丁基亚硝酸酯和${\mathrm{B}}_{2}{\text{ pin }}_{2}$的量，可以实现选择性单硼化或双硼化(4bh和4bi)。

Scheme 2. Comparison of Yields with Those Reported Previously ${}^{a}$

方案2. 与之前报道产率的比较${}^{a}$

${}^{a}$ Current reaction conditions: arylamine $\left( {1\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}({1.1}$ mmol), t-BuONO (1.5 mmol), MeCN (3 mL), 80 ${}^{ \circ }\mathrm{C}$ , 2 h. ${}^{b}$ Isolated yield. The figure in brackets refers to the yields reported under the previous reaction conditions; see ref 11. The previous reaction conditions: arylamine $\left( {1\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right) , t$ -BuONO (1.5 mmol), BPO (2 mol %), MeCN (3 mL), room temperature, 2 h.

${}^{a}$ 当前反应条件:芳胺$\left( {1\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}({1.1}$毫摩尔)，叔丁基亚硝酸酯(1.5毫摩尔)，乙腈(3毫升)，80${}^{ \circ }\mathrm{C}$，2小时。${}^{b}$ 分离产率。括号中的数字指的是在前述反应条件下报道的产率；见参考文献11。前述反应条件:芳胺$\left( {1\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right) , t$-叔丁基亚硝酸酯(1.5毫摩尔)，过氧化苯甲酰(2摩尔%)，乙腈(3毫升)，室温，2小时。

Scheme 3. Scope of para-Substitued Aniline Derivatives ${}^{a}$

方案3. 对-取代苯胺衍生物的范围${}^{a}$

${}^{a}$ Reaction conditions: arylamine $\left( {1\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right) , t$ - BuONO (1.5 mmol), MeCN (3 mL), 2 h. ${}^{b}$ Isolated yield. ${}^{c}t$ -BuONO (1.1 mmol). ${}^{d}{\mathrm{\;B}}_{2}{\mathrm{{pin}}}_{2}$ (2.2 mmol), $t$ -BuONO (3 mmol).

${}^{a}$反应条件:芳胺$\left( {1\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right) , t$-叔丁基亚硝酸酯(1.5毫摩尔)，乙腈(3毫升)，2小时。${}^{b}$分离产率。${}^{c}t$-叔丁基亚硝酸酯(1.1毫摩尔)。${}^{d}{\mathrm{\;B}}_{2}{\mathrm{{pin}}}_{2}$(2.2毫摩尔)，$t$-叔丁基亚硝酸酯(3毫摩尔)。

Furthermore, we expanded the scope of substrates to meta-, ortho-, or multi-substituted arylamine substrates (Scheme 4). The borylation in general affords relatively low to moderate yields. Compared with electron-rich aniline derivatives, electron-deficient ones usually give higher yields when the corresponding borylation products are stable toward column chromatography (for example, 4cj, 4ck, and 4cn). Moreover, the steric bulkiness of the ortho substitution seems to affect the borylation reaction. The substrates with ortho substitution generally afforded diminished yields. For example, reaction with 2,6-dimethylaniline gave only 23% yield (4cd).

此外，我们将底物范围扩展至间位、邻位或多取代芳胺底物(方案4)。一般来说，硼化反应的产率相对较低至中等。与富电子的苯胺衍生物相比，当相应的硼化产物对柱色谱稳定时(例如4cj、4ck和4cn)，缺电子的苯胺衍生物通常产率更高。此外，邻位取代基的空间位阻似乎会影响硼化反应。具有邻位取代的底物通常产率降低。例如，与2,6-二甲基苯胺反应的产率仅为23%(4cd)。

Scheme 4. Reaction with meta, ortho, or multi-Substitued Arylamines ${}^{a}$

方案4. 与间位、邻位或多取代芳胺的反应${}^{a}$

“Reaction conditions: arylamine $\left( {1\mathrm{\;{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{\;{mmol}}}\right) , t$ - BuONO (1.5 mmol), MeCN (3 mL), 2 h. ${}^{b}$ Isolated yield.

“反应条件:芳胺$\left( {1\mathrm{\;{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{\;{mmol}}}\right) , t$ - 叔丁基亚硝酸酯(1.5 mmol)，乙腈(3 mL)，2小时。${}^{b}$ 分离产率。

Subsequently, we proceeded to extend the reaction to some complicated aromatic amines and heterocyclic amines. These results are shown in Scheme 5. The reaction with 2- aminonaphthalene afforded 5da with low yield, and large amount of ${\mathrm{B}}_{2}{\text{ pin }}_{2}$ was recovered. This is likely due to the facile oxidation of 2-aminonaphthalene under the reaction conditions. In the case of 5db and 5dc, the low yields are attributed to the instability of these products.

随后，我们着手将该反应扩展到一些复杂的芳香胺和杂环胺。这些结果如图5所示。与2-氨基萘的反应产率较低，得到了5da，并回收了大量的${\mathrm{B}}_{2}{\text{ pin }}_{2}$。这可能是由于2-氨基萘在反应条件下容易氧化。对于5db和5dc，低产率归因于这些产物的不稳定性。

Heterocyclic boronic acids or boronates have found wide applications in organic synthesis, especially for pharmaceuticals. However, these boron compounds are usually not easy to synthesize as a result of the limitations of other methodologies that have been discussed in the Introduction. Thus, we investigated the application of this new borylation method to access heterocyclic boronates. We found that electron-deficient heterocyclic amines demonstrate high reactivity with nearly complete conversion of ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ . However, electron-rich heterocyclic amines are prone to be oxidized in the presence of $t$ -BuONO, resulting in low yields of borylation products (5de and 5df).

杂环硼酸或硼酸酯在有机合成中有着广泛的应用，尤其是在制药领域。然而，由于引言中所讨论的其他方法的局限性，这些硼化合物通常不易合成。因此，我们研究了这种新的硼化方法在制备杂环硼酸酯中的应用。我们发现缺电子杂环胺表现出高反应活性，${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ 的转化率几乎达到100%。然而，富电子杂环胺在$t$-BuONO存在下容易被氧化，导致硼化产物(5de和5df)的产率较低。

Scheme 5. Scope of Other Aromatic Derivatives ${}^{a}$

方案5. 其他芳香族衍生物的范围${}^{a}$

${}^{a}$ Reaction conditions: arylamine (1 mmol), ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ (1.1 mmol), $t$ - BuONO (1.5 mmol), 2 h, MeCN (3 mL). ${}^{b}$ Isolated yield. ${}^{c}$ The isolated yield of 5da in brackets refer to the reaction in water: a mixture of arylamine $\left( {1\mathrm{\;{mmol}}}\right) ,{\mathrm{{NaNO}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right) ,\mathrm{{HCl}}({0.41}\mathrm{\;{mL}}$ , ${12}\mathrm{\;{mol}}/\mathrm{L})$ , and ${\mathrm{H}}_{2}\mathrm{O}\left( {1\mathrm{\;{mL}}}\right)$ was stirred at $0{}^{ \circ }\mathrm{C}$ for ${15}\mathrm{\;{min}}$ , then to the mixture was added ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right)$ in $\mathrm{{MeCN}}\left( {1\mathrm{{mL}}}\right)$ , and stirring was continued at ${80}^{ \circ }\mathrm{C}$ for $2\mathrm{\;h}.{}^{d}$ Arylamine $\left( {{0.5}\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ (1.1 equiv), $t$ -BuONO (1.5 equiv), MeCN (1.5 mL),2 h. ${}^{e}$ Isolated by recrystallization. ${}^{f}$ Yields in brackets refer to GC yield measured with a GC-MS instrument (mesitylene as internal standard).

${}^{a}$反应条件:芳基胺(1 mmol)，${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$(1.1 mmol)，$t$-叔丁基亚硝酸酯(1.5 mmol)，2小时，乙腈(3 mL)。${}^{b}$分离产率。${}^{c}$括号内5da的分离产率指在水中的反应:将芳基胺$\left( {1\mathrm{\;{mmol}}}\right) ,{\mathrm{{NaNO}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right) ,\mathrm{{HCl}}({0.41}\mathrm{\;{mL}}$、${12}\mathrm{\;{mol}}/\mathrm{L})$和${\mathrm{H}}_{2}\mathrm{O}\left( {1\mathrm{\;{mL}}}\right)$的混合物在$0{}^{ \circ }\mathrm{C}$搅拌${15}\mathrm{\;{min}}$，然后向混合物中加入溶于$\mathrm{{MeCN}}\left( {1\mathrm{{mL}}}\right)$的${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}}}\right)$，并在${80}^{ \circ }\mathrm{C}$继续搅拌$2\mathrm{\;h}.{}^{d}$。芳基胺$\left( {{0.5}\mathrm{{mmol}}}\right) ,{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$(1.1当量)，$t$-叔丁基亚硝酸酯(1.5当量)，乙腈(1.5 mL)，2小时。${}^{e}$通过重结晶分离。${}^{f}$括号内产率指用气相色谱-质谱联用仪(以均三甲苯为内标)测得的气相色谱产率。

It is noteworthy that most of the heterocyclic boronates are not stable on silica gel column chromatography. To simplify the synthetic procedure and in particular to avoid the problem of product decomposition during the purification process, a sequential borylation and Pd-catalyzed cross-coupling reaction has been demonstrated in our preliminary communication. ${}^{11}$ Such a sequential process avoids the troublesome purification process and significantly strengthens the usefulness of this new borylation method. Herein we further expand the scope of this sequential process, especially for the heterocyclic substrates (Scheme 6). Thus, upon completion of the borylation, MeCN is removed under reduced pressure to give crude borylation product, which is then subjected next to Pd-catalyzed Suzuki-Miyaura cross-coupling reaction without further purification to afford coupling products in moderately high yields in general. However, in some cases the yields are less satisfactory (6d, 6h, 6r, and 6s).

值得注意的是，大多数杂环硼酸酯在硅胶柱色谱上不稳定。为了简化合成步骤，特别是避免在纯化过程中产物分解的问题，我们在初步通讯中展示了一种顺序硼化和钯催化的交叉偶联反应。${}^{11}$这样的顺序过程避免了麻烦的纯化过程，并显著增强了这种新硼化方法的实用性。在此，我们进一步扩展了这种顺序过程的范围，特别是对于杂环底物(方案6)。因此，硼化反应完成后，在减压下除去乙腈得到粗硼化产物，然后将其直接进行钯催化的铃木-宫浦交叉偶联反应，无需进一步纯化，一般能以中等偏高产率得到偶联产物。然而，在某些情况下产率不太令人满意(6d、6h、6r和6s)。

Finally, to demonstrate the practical usefulness of this borylation method, the reaction has been carried out in gram-scale for selected substrates. As shown in Scheme 7, the reaction provided the desired boronates in good yields. The sequential borylation and Pd-catalyzed cross-coupling has also been scaled up (eq 1).

最后，为了证明这种硼化方法的实际实用性，对选定的底物进行了克级规模的反应。如图7所示，反应以良好的产率提供了所需的硼酸酯。顺序硼化和钯催化的交叉偶联也已扩大规模(式1)。

(1)

Since it is well documented that Sandmeyer reaction proceeds through a radical mechanism, ${}^{{13}\mathrm{\;b},{15}}$ a possible reaction pathway involving radical species is proposed for this borylation reaction as shown in Scheme 8. First, the tert-butoxide anion interacts with ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ to form a tetra-coordinated boron

由于有充分的文献记载桑德迈尔反应是通过自由基机理进行的，${}^{{13}\mathrm{\;b},{15}}$如图8所示，为这种硼化反应提出了一种可能涉及自由基物种的反应途径。首先，叔丁醇根阴离子与${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$相互作用形成四配位硼

Scheme 6. Sequential Borylation and Pd-Catalyzed Cross-Coupling Reaction ${}^{a}$

方案6. 顺序硼化和钯催化的交叉偶联反应 ${}^{a}$

${}^{a}$ Reaction condition for the first step: arylamine (1 mmol), ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ (1.1 mmol), t-BuONO (1.5 mmol), 2 h; second step: DMF (1.5 mL). ${}^{b}$ Isolated yield. ${}^{c}$ Reaction conditions for the second step: $\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}$ (5 mmol %), 10% aq ${\mathrm{{Na}}}_{2}{\mathrm{{CO}}}_{3}\left( {2\mathrm{\;{mL}}}\right)$ , toluene (4 mL), EtOH (2 mL), 12 h.

${}^{a}$第一步反应条件:芳基胺(1 mmol)，${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$(1.1 mmol)，叔丁基亚硝酸酯(1.5 mmol)，2小时；第二步:N, N-二甲基甲酰胺(1.5 mL)。${}^{b}$分离产率。${}^{c}$第二步反应条件:$\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}$(5 mmol%)，10% 质量分数的 ${\mathrm{{Na}}}_{2}{\mathrm{{CO}}}_{3}\left( {2\mathrm{\;{mL}}}\right)$，甲苯(4 mL)，乙醇(2 mL)，12小时。

Scheme 7. Gram-Scale Experiments ${}^{a}$

方案7. 克级实验 ${}^{a}$

${}^{a}$ Reaction conditions: arylamine (20 mmol), ${\mathrm{B}}_{2}{\text{ pin }}_{2}$ (1.05 equiv), $t$ - BuONO (1.5 equiv),12 h, MeCN (60 mL). ${}^{b}$ Isolated yield. ${}^{c}$ Arylamine (10 mmol).

${}^{a}$反应条件:芳基胺(20 mmol)，${\mathrm{B}}_{2}{\text{ pin }}_{2}$(1.05当量)，$t$叔丁基亚硝酸酯(1.5当量)，12小时，乙腈(60 mL)。${}^{b}$分离产率。${}^{c}$芳基胺(10 mmol)。

Scheme 8. Possible Reaction Mechanism

方案8. 可能的反应机理

complex A. Single electron transfer (SET) between ate complex A and aryldiazonium ion is then followed to afford aryl radical D through ${\mathrm{N}}_{2}$ extrusion from radical B. Finally, reaction of aryl radical $\mathbf{D}$ with intermediate $\mathbf{C}$ gives the borylation product.

配合物A。然后，在配合物A和芳基重氮离子之间发生单电子转移(SET)，通过从自由基B中挤出${\mathrm{N}}_{2}$得到芳基自由基D。最后，芳基自由基$\mathbf{D}$与中间体$\mathbf{C}$反应得到硼化产物。

This reaction mechanism is substantiated by the following experimental observations: (1) When the borylation was carried out in the presence of 1.5 equiv of the radical scavenger TEMPO, the reaction became sluggish and phenylboronate was formed in only 8% yield after 4 h, while a control experiment has demonstrated that TEMPO does not react directly with ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ under these conditions (eq 2). (2) Heating a 1:1 mixture

该反应机理由以下实验观察结果证实:(1) 当硼化反应在1.5当量的自由基清除剂TEMPO存在下进行时，反应变得缓慢，4小时后苯基硼酸酯的产率仅为8%，而对照实验表明，在这些条件下TEMPO不会直接与${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$反应(方程式2)。(2) 加热1:1的混合物

of BPO and ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ in MeCN at ${100}{}^{ \circ }\mathrm{C}$ for $4\mathrm{\;h}$ affords the phenylboronate in 37% yield (eq 3). It is known that BPO

然而，当将${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$设定为与通过另一种方法(碘化苯、${100}{}^{ \circ }\mathrm{C}$和偶氮二异丁腈)产生的苯基自由基反应时，$4\mathrm{\;h}$产物Ph-Bpin的产率仅为7%(方程式4)。因此，尽管大多数实验

cleaves under thermolytic conditions to benzoic acid radical upon heating, which generates phenyl radical by further decomposition. Thus, the desired product is likely formed by the reaction of benzoic acid radical and/or phenyl radical with ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ . (3) EPR experiments provide supportive evidence for a radical process. ${}^{16}$

在热解条件下加热时会裂解为苯甲酸自由基，该自由基通过进一步分解产生苯基自由基。因此，所需产物可能是由苯甲酸自由基和/或苯基自由基与${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$反应形成的。(3)电子顺磁共振实验为自由基过程提供了支持性证据。${}^{16}$

However, when ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ was set to react with phenyl radical, which was generated by an alternative process (PhI, $n - {\mathrm{{Bu}}}_{3}\mathrm{{SnH}}$ , and AIBN), ${}^{17}$ the product Ph-Bpin was formed only in 7% yield (eq 4). Consequently, even though most of the experimental

然而，当${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$与通过另一种方法(PhI、$n - {\mathrm{{Bu}}}_{3}\mathrm{{SnH}}$和AIBN)产生的苯基自由基反应时，${}^{17}$产物Ph-Bpin的产率仅为7%(方程式4)。因此，即使大多数实验

0.2 equiv 5%

观察结果与方案8所示的机理一致，但涉及离子过程的替代机理，如硼酸盐配合物对芳基重氮盐的亲核芳香取代，不能完全排除。需要进一步严格研究以明确确定反应机理。

observations are consistent with the mechanism shown in Scheme 8, alternative mechanisms involving an ionic process, such as nucleophilic aromatic substitution of the aryldiazonium salt by the boron ate complex, cannot be completely ruled out. Further rigorous investigation is required to unambiguously establish the reaction mechanism.

观察结果与方案8所示的机理一致，但涉及离子过程的替代机理，如硼酸盐配合物对芳基重氮盐的亲核芳香取代，不能完全排除。需要进一步严格研究以明确确定反应机理。

CONCLUSION

结论

In this report we have further optimized the metal-free deaminoborylation reaction. The yields are improved, and the substrate scope has been significantly expanded, especially to heterocyclic amine derivatives, for which the corresponding boronate products are highly important both in academic research and in the pharmaceutical industry. A radical mechanism involving SET between aryldiazonium ion and tetra-coordinated boron complex has been proposed. Since arylamines are inexpensive and ubiquitous starting materials, this borylation method is expected to find wide applications in organic synthesis.

在本报告中，我们进一步优化了无金属脱氨基硼化反应。产率得到了提高，底物范围也显著扩大，尤其是对于杂环胺衍生物，其相应的硼酸酯产物在学术研究和制药行业中都非常重要。我们提出了一种涉及芳基重氮离子与四配位硼配合物之间单电子转移的自由基机理。由于芳胺是廉价且普遍存在的起始原料，这种硼化方法有望在有机合成中得到广泛应用。

EXPERIMENTAL SECTION

实验部分

The solvents were all distilled prior to use. MeCN and DMF were distilled from calcium hydride. Silica gel, 200-300 mesh, was used for the chromatography. ${}^{1}\mathrm{H}$ NMR (400 MHz) and ${}^{13}\mathrm{C}$ NMR (100 MHz) spectra were recorded in ppm using tetramethylsilane (TMS) as the internal standard; IR spectra are reported in wave numbers, ${\mathrm{{cm}}}^{-1}$ . For HRMS measurements, the mass analyzer is FT-ICR. Melting points are reported as uncorrected.

所用溶剂均在使用前进行了蒸馏。乙腈和N, N -二甲基甲酰胺从氢化钙中蒸馏得到。使用200 - 300目的硅胶进行柱色谱分离。${}^{1}\mathrm{H}$核磁共振(400兆赫兹)和${}^{13}\mathrm{C}$核磁共振(100兆赫兹)谱以百万分之一为单位记录，以四甲基硅烷(TMS)作为内标；红外光谱以波数${\mathrm{{cm}}}^{-1}$报告。对于高分辨质谱测量，质量分析器为傅里叶变换离子回旋共振质谱仪。熔点报告为未经校正的值。

Typical Procedure of Borylation Reaction. ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ (279 mg,1.1 mmol) and 2-aminobenzonitrile (1aa, 118 mg, 1.0 mmol) were weighed in a ${25}\mathrm{\;{mL}}$ round-bottom flask. MeCN (3 mL) and $t$ -BuONO (2a, 155 mg, 1.5 mmol) were then added in succession. The resulting reaction solution was stirred for $2\mathrm{\;h}$ at ${80}^{ \circ }\mathrm{C}\left( {\mathrm{N}}_{2}\right.$ evolution completed within 5 to ${15}\mathrm{\;{min}}$ ). The solution was then concentrated under reduced pressure, and the crude residue was purified by flash chromatography (silica gel, petroleum ether/EtOAc = 200:1). 2- (4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile ${\left( 4aa\right) }^{11}$ was obtained (152 mg, 66%) as pale yellow solid; mp 80-82 ${}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 7.89}\left( {\mathrm{{dd}}, J = {1.2},{7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.70}(\mathrm{{dd}}, J = {1.2}$ , 7.5 Hz, 1H), 7.55 (m, 2H), 1.39 (s, 12H); ${}^{13}$ C NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 135.8, 133.4, 131.5, 131.0, 118.9, 117.3, 84.8, 24.8; IR (film) 2981 (w), 2228 (w), 1488 (w), 1441 (m), 1382 (s), 1356 (s), 1143 $\left( \mathrm{m}\right) ,{1119}\left( \mathrm{\;m}\right) ,{857}\left( \mathrm{\;m}\right) ,{731}\left( \mathrm{\;m}\right) ,{654}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 229 (M*, 24), 214 (46), 188 (50), 186 (61), 171 (45), 130 (100), 129 (29), 103 (24), 85 (17).

硼酸酯化反应的典型步骤。将${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$(279毫克，1.1毫摩尔)和2 -氨基苯甲腈(1aa，118毫克，1.0毫摩尔)称入一个${25}\mathrm{\;{mL}}$圆底烧瓶中。然后依次加入乙腈(3毫升)和$t$ -亚硝酸叔丁酯(2a，155毫克，1.5毫摩尔)。所得反应溶液在${80}^{ \circ }\mathrm{C}\left( {\mathrm{N}}_{2}\right.$搅拌$2\mathrm{\;h}$，直至在5至${15}\mathrm{\;{min}}$内气体逸出完全。然后将溶液在减压下浓缩，粗残余物通过快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 200:1)纯化。得到2 -(4,4,5,5 -四甲基 - 1,3,2 -二氧硼戊环 - 2 -基)苯甲腈${\left( 4aa\right) }^{11}$(152毫克，66%)，为浅黄色固体；熔点80 - 82${}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 7.89}\left( {\mathrm{{dd}}, J = {1.2},{7.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.70}(\mathrm{{dd}}, J = {1.2}$，7.5赫兹，1H)，7.55(多重峰，2H)，1.39(单峰，12H)；${}^{13}$碳核磁共振(100兆赫兹，CDCl${}_{3}$)$\delta$135.8，133.4，131.5，131.0，118.9，117.3，84.8，24.8；红外(薄膜)2981(弱)，2228(弱)，1488(弱)，1441(中)，1382(强)，1356(强)，1143$\left( \mathrm{m}\right) ,{1119}\left( \mathrm{\;m}\right) ,{857}\left( \mathrm{\;m}\right) ,{731}\left( \mathrm{\;m}\right) ,{654}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)229(M*，24)，214(46)，188(50)，186(61)，171(45)，130(100)，129(29)，103(24)，85(17)。

2-(4-Fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ab). ${}^{11}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4ab (169 mg,76%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDC ${\mathrm{L}}_{3}$ ) $\delta {{7.80}\mathrm{\;\left( {t, J = {7.2}\mathrm{{Hz}},2\mathrm{H}}\right) }},{7.04}\mathrm{\;\left( {t, J = {8.8}\mathrm{{Hz}},2\mathrm{H}}\right) },{1.33}$ (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 165.1 (d, J = 250.3 Hz), 137.0 (d, J = 8.2 Hz), 114.8 (d, J = 20.3 Hz), 83.8, 24.8; IR (film) 2980 (w), 1603 (m), 1399 (m), 1361 (s), 1143 (m), 1088 (m), 860 (w), 668 (w) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 222 (M ${}^{ + }$ , 21), 207 (87), 136 (41), 123 (100), 122 (31), 85 (14).

2-(4-氟苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷(4ab)。${}^{11}$ 快速柱色谱法(硅胶,石油醚/乙酸乙酯=500:1)得到4ab(169毫克,76%);浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫, CDC ${\mathrm{L}}_{3}$ ) $\delta {{7.80}\mathrm{\;\left( {t, J = {7.2}\mathrm{{Hz}},2\mathrm{H}}\right) }},{7.04}\mathrm{\;\left( {t, J = {8.8}\mathrm{{Hz}},2\mathrm{H}}\right) },{1.33}$ (单峰,12H);${}^{13}\mathrm{C}$ 核磁共振(100兆赫, CDCl ${}_{3}$ ) δ 165.1(双峰, J = 250.3赫兹),137.0(双峰, J = 8.2赫兹),114.8(双峰, J = 20.3赫兹),83.8,24.8;红外(薄膜)2980(弱),1603(中),1399(中),1361(强),1143(中),1088(中),860(弱),668(弱)厘米${}^{-1}$ ;电子轰击质谱(质荷比,相对强度)222(M ${}^{ + }$ ,21),207(87),136(41),123(100),122(31),85(14)。

2-(4-Chlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ac). ${}^{11}$ Flash chromatography (silica gel, petroleum ether, then petroleum ether/EtOAc = 200:1) afforded 4ac (160 mg, 67%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl, ${}_{3}\delta$ 7.73 (d, $J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${7.33}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta$ 137.5,136.1,127.9,83.9,24.8; IR (film) 2979 (w),1597 (m),1393 (m), 1360 (s), 1144 (m), 1094 (s), 1017 (m), 858 (m) cm ${}^{-1}$ ; EI-MS ( $m/z$ , relative intensity) 240 (13), ${238}\left( {{\mathrm{\;M}}^{ + },{38}}\right) ,{225}\left( {34}\right) ,{223}\left( {100}\right)$ , 152 (63), 141 (33), 139 (95).

2-(4-氯苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷(4ac)。${}^{11}$ 快速柱色谱法(硅胶,石油醚,然后石油醚/乙酸乙酯=200:1)得到4ac(160毫克,67%);浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫, CDCl, ${}_{3}\delta$ 7.73(双峰,$J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}$ ),${7.33}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta$ 137.5,136.1,127.9,83.9,24.8;红外(薄膜)2979(弱),1597(中),1393(中),1360(强),1144(中),1094(强),1017(中),858(中)厘米${}^{-1}$ ;电子轰击质谱($m/z$ ,相对强度)240(13),${238}\left( {{\mathrm{\;M}}^{ + },{38}}\right) ,{225}\left( {34}\right) ,{223}\left( {100}\right)$ ,152(63),141(33),139(95)。

4,4,5,5-Tetramethyl-2-o-tolyl-1,3,2-dioxaborolane (4ad). ${}^{11}$ Flash chromatography (silica gel, then petroleum ether/EtOAc $= {500} : 1$ ) afforded 4ad $\left( {{126}\mathrm{{mg}},{58}\% }\right)$ ; white solid; mp ${32} - {34}{}^{ \circ }\mathrm{C}.{}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {7.78} - {7.74}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.30}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.16}(\mathrm{\;m}$ , 2H), 2.53 (s, 3H), 1.33 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 144.8, 135.8, 130.7, 129.7, 124.7, 83.4, 24.9, 22.2; IR (film) 2978 (w), 2926 (w), 1380 (m), 1346 (s), 1146 (m), 1073 (m), 862 (m), 730 (m), 659 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 218 (M ${}^{ + }$ , 25), 203 (35), 161 (85), 119 (100), 118 (84), 91 (20).

4,4,5,5-四甲基-2-邻甲苯基-1,3,2-二氧杂硼烷(4ad)。${}^{11}$ 通过快速柱色谱法(硅胶，然后是石油醚/乙酸乙酯$= {500} : 1$ )得到4ad$\left( {{126}\mathrm{{mg}},{58}\% }\right)$ ；白色固体；熔点${32} - {34}{}^{ \circ }\mathrm{C}.{}^{1}\mathrm{H}$ 核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {7.78} - {7.74}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.30}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.16}(\mathrm{\;m}$ ，2H)，2.53(单峰，3H)，1.33(单峰，12H)；${}^{13}\mathrm{C}$ 核磁共振(100兆赫兹，CDCl${}_{3}$ )δ144.8，135.8，130.7，129.7，124.7，83.4，24.9，22.2；红外光谱(薄膜)2978(弱)，2926(弱)，1380(中)，1346(强)，1146(中)，1073(中)，862(中)，730(中)，659(中)厘米${}^{-1}$ ；电子轰击质谱(m/z，相对强度)218(M${}^{ + }$ ，25)，203(35)，161(85)，119(100)，118(84)，91(20)。

4,4,5,5-Tetramethyl-2-p-tolyl-1,3,2-dioxaborolane (4ae). ${}^{11}$ Flash chromatography (silica gel, petroleum ether, then petroleum ether/ EtOAc = 250:1) afforded 4ae (163 mg, 75%); white solid; mp 53-54 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.70 (d, $J = {7.7}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${7.17}(\mathrm{\;d}, J \; = {7.7}\mathrm{\;{Hz}},2\mathrm{H}),{2.35}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 141.3,134.8,128.4,83.5,24.8,21.6; IR (film) 2978 (w), 1613 (w), 1517 (w), 1398 (m), 1360 (s), 1318 (m), 1304 (w), 1144 (m), 860 (m) cm ${\mathrm{{cm}}}^{-1}$ ; EI-MS ( $m/z$ , relative intensity) 218 ( ${\mathrm{M}}^{ + }$ , 44), 203 (61), 132 (67), 119 (100), 118 (50), 91 (17).

4,4,5,5-四甲基-2-对甲苯基-1,3,2-二氧杂硼烷(4ae)。${}^{11}$ 通过快速柱色谱法(硅胶，石油醚，然后石油醚/乙酸乙酯 = 250:1)得到4ae(163毫克，75%)；白色固体；熔点53 - 54${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 7.70(双峰，$J = {7.7}\mathrm{\;{Hz}},2\mathrm{H}$ )，${7.17}(\mathrm{\;d}, J \; = {7.7}\mathrm{\;{Hz}},2\mathrm{H}),{2.35}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 141.3，134.8，128.4，83.5，24.8，21.6；红外光谱(薄膜)2978(弱)，1613(弱)，1517(弱)，1398(中)，1360(强)，1318(中)，1304(弱)，1144(中)，860(中)厘米${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱($m/z$ ，相对强度)218(${\mathrm{M}}^{ + }$ ，44)，203(61)，132(67)，119(100)，118(50)，91(17)。

2-(4-Bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4af). ${}^{11}$ Flash chromatography (silica gel, petroleum ether, then petroleum ether/EtOAc = 500:1) afforded 4af (147 mg, 52%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 7.66 (d, $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${7.50}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta$ 136.3,130.9,126.2,84.0,24.8; IR (film) 2978 (w),1589 (m),1389 (m), 1359 (s), 1166 (m), 1144 (m), 1089 (s), 1012 (m), 821 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 284 (51),282 }\left( {{\mathrm{M}}^{ + },{50}}\right) ,{269}}\right) \; \left( {100}\right) ,{267}\left( {100}\right) ,{198}\left( {71}\right) ,{196}\left( {72}\right) ,{185}\left( {89}\right) ,{183}\left( {96}\right) ,{103}\left( {36}\right)$ .

2-(4-溴苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷(4af)。${}^{11}$ 快速柱色谱法(硅胶，石油醚，然后石油醚/乙酸乙酯=500:1)得到4af(147mg，52%);浅黄色液体。${}^{1}\mathrm{H}$ NMR(400MHz，CDCl${}_{3}$)δ7.66(d，$J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}$)，${7.50}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta$ 136.3,130.9,126.2,84.0,24.8;IR(薄膜)2978(w)，1589(m)，1389(m)，1359(s)，1166(m)，1144(m)，1089(s)，1012(m)，821(m) ${\mathrm{{cm}}}^{-1}$;EI-MS$\left( {m/z\text{ , relative intensity) 284 (51),282 }\left( {{\mathrm{M}}^{ + },{50}}\right) ,{269}}\right) \; \left( {100}\right) ,{267}\left( {100}\right) ,{198}\left( {71}\right) ,{196}\left( {72}\right) ,{185}\left( {89}\right) ,{183}\left( {96}\right) ,{103}\left( {36}\right)$。

4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (4ag). ${}^{11}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 30:1 then 0:1) afforded 4ag (153 mg, 67%); pale yellow solid; mp 93- ${95}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.88 (d, $J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.64 (d, $J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}),{1.35}$ (s,12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 135.1, 131.1, 118.8, 114.5, 84.4, 24.8; IR (film) 2980 (w), 2229 (w), 1398 (m), 1360 (s), 1168 (m), 1143 (s), 1125 (m), 1088 (s), 668 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS ( $m/z$ , relative intensity) 229 ( ${\mathrm{M}}^{ + },{14}),{214}$ (100),213 (20), 186 (12), 143 (81), 130 (50), 58 (16).

4-(4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷-2-基)苯甲腈(4ag)。${}^{11}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=30:1然后0:1)得到4ag(153mg，67%);浅黄色固体;熔点93-${95}^{ \circ }\mathrm{C}$。${}^{1}\mathrm{H}$ NMR(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 7.88(d，$J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}$)，7.64(d，$J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}),{1.35}$(s，12H);${}^{13}\mathrm{C}$ NMR(100MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 135.1,131.1,118.8,114.5,84.4,24.8;IR(薄膜)2980(w)，2229(w)，1398(m)，1360(s)，1168(m)，1143(s)，1125(m)，1088(s)，668(m) ${\mathrm{{cm}}}^{-1}$;EI-MS($m/z$，相对强度)229(${\mathrm{M}}^{ + },{14}),{214}$(100)，213(20)，186(12)，143(81)，130(50)，58(16)。

2-(3,4-Dichlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ah). ${}^{11}$ Flash chromatography (silica gel, petroleum ether) afforded 4ah (194 mg, 71%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.86 $\left( {\mathrm{s},1\mathrm{H}}\right) ,{7.60}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.43}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.33}$ (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 136.5, 135.5, 133.7, 132.2, 130.0, 84.3, 24.8; IR (film) 2978 (w), 1590 (w), 1381 (m), 1354 (s), ${1143}\left( \mathrm{\;m}\right) ,{1094}\left( \mathrm{\;m}\right) ,{1032}\left( \mathrm{\;w}\right) ,{867}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 274 (31), 272 ( ${\mathrm{M}}^{ + }$ , 46), 259 (69), 257 (100), 188 (65), 186 (95), 175 (48), 173 (84), 85 (23).

2-(3,4-二氯苯基)-4,4,5,5-四甲基-1,3,2-二氧硼戊环(4ah)。${}^{11}$ 快速柱色谱法(硅胶,石油醚)得到4ah(194mg,71%);浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫,${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.86 $\left( {\mathrm{s},1\mathrm{H}}\right) ,{7.60}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.43}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.33}$ (单峰,12H);${}^{13}\mathrm{C}$ 核磁共振(100兆赫, CDCl ${}_{3}$ ) $\delta$ 136.5,135.5,133.7,132.2,130.0,84.3,24.8;红外光谱(薄膜)2978(弱),1590(弱),1381(中),1354(强),${1143}\left( \mathrm{\;m}\right) ,{1094}\left( \mathrm{\;m}\right) ,{1032}\left( \mathrm{\;w}\right) ,{867}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ;电子轰击质谱 $(m/z$ ,相对强度)274(31),272( ${\mathrm{M}}^{ + }$ ,46),259(69),257(100),188(65),186(95),175(48),173(84),85(23)。

4,4,5,5-Tetramethyl-2-(4-(methylthio)phenyl)-1,3,2-dioxaboro-lane (4ba). ${}^{18}$ Flash chromatography (silica gel, petroleum ether/ EtOAc = 500:1) afforded 4ba (160 mg,64%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) 67.71 (d, J = 7.8 Hz, 2H), 7.22 (d, J = 7.8 Hz, 2H), 2.47 (s, 3H), 1.33 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 142.5, 135.0, 125.0, 83.6, 24.8, 15.0; IR (film) 2978 (w), 1597 (m), 1395 (m), 1359 (s), 1327 (m), 1103 (s), 859 (m), 668 (m) cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 250 ( }{\mathrm{M}}^{ + },{100}}\right) ,{249}$ (28),235 (29),164 (30), 151 (63), 150 (95).

4,4,5,5-四甲基-2-(4-(甲硫基)苯基)-1,3,2-二氧硼戊环(4ba)。${}^{18}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4ba(160毫克，64%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫，CDCl3) δ7.71(d，J = 7.8赫兹，2H)，7.22(d，J = 7.8赫兹，2H)，2.47(s，3H)，1.33(s，12H)；${}^{13}\mathrm{C}$ 核磁共振(100兆赫，CDCl ${}_{3}$ ) $\delta$ 142.5，135.0，125.0，83.6，24.8，15.0；红外光谱(薄膜)2978(弱)，1597(中)，1395(中)，1359(强)，1327(中)，1103(强)，859(中)，668(中)厘米${}^{-1}$ ；电子轰击质谱$\left( {m/z\text{ , relative intensity) 250 ( }{\mathrm{M}}^{ + },{100}}\right) ,{249}$ (28)，235(29)，164(30)，151(63)，150(95)。

4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (4bb). ${}^{19}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 10:1) afforded 4bb (145 mg,66%); pale yellow solid; mp 113-114 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl, 3) 67.68 (d, J = 8.0 Hz, 2H), 6.81 (d, J = 8.0 $\mathrm{{Hz}},2\mathrm{H}),{6.68}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) 6 158.7, 136.7, 115.0, 83.9, 24.7; IR (film) 3364 (w), 2979 (w), 1607 (s), 1397 (m), 1358 (s), 1170 (m), 1141 (s), 1084 (m), 670 (m) cm ${}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) ${220}\left( {{\mathrm{M}}^{ + },{48}),{205}\left( {58}\right) ,{134}\left( {40}\right) ,{121}}\right.$ (100), 120 (97).

4-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯酚(4bb)。${}^{19}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=10:1)得到4bb(145毫克，66%)；浅黄色固体；熔点113 - 114${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫兹，CDCl₃)δ7.68(d，J = 8.0赫兹，2H)，6.81(d，J = 8.0$\mathrm{{Hz}},2\mathrm{H}),{6.68}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫兹，${\mathrm{{CDCl}}}_{3}$ )δ158.7，136.7，115.0，83.9，24.7；红外光谱(薄膜)3364(w)，2979(w)，1607(s)，1397(m)，1358(s)，1170(m)，1141(s)，1084(m)，670(m)厘米${}^{-1}$ ；电子轰击质谱$\left( {m/z}\right.$ ，相对强度)${220}\left( {{\mathrm{M}}^{ + },{48}),{205}\left( {58}\right) ,{134}\left( {40}\right) ,{121}}\right.$ (100)，120(97)。

4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (4bc). ${}^{20}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 20:1) afforded 4bc (121 mg, 52%); pale yellow solid; mp 55-58 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) $\delta$ 10.05 (s,1H),7.97 (d, $J = \; {7.9}\mathrm{\;{Hz}},2\mathrm{H}),{7.86}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 192.5, 138.0, 135.2, 128.6, 84.2, 24.8; IR (film) 2979 (w), 1707 (s), 1508 (m), 1358 (s), 1169 (m), 1086 (s), 857 (m), 825 (m), 800 (m) cm ${}^{-1}$ ; EI-MS ( $m/z$ , relative intensity) 232 ( ${\mathrm{M}}^{ + },{21}$ ), 217 (78), 146 (90), 133 (100), 85 (25).

4-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯甲醛(4bc)。${}^{20}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1然后20:1)得到4bc(121毫克，52%)；浅黄色固体；熔点55 - 58${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫兹，CDCl₃)$\delta$ 10.05(s，1H)，7.97(d，$J = \; {7.9}\mathrm{\;{Hz}},2\mathrm{H}),{7.86}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫兹，CDCl${}_{3}$ )δ192.5，138.0，135.2，128.6，84.2，24.8；红外光谱(薄膜)2979(w)，1707(s)，1508(m)，1358(s)，1169(m)，1086(s)，857(m)，825(m)，800(m)厘米${}^{-1}$ ；电子轰击质谱($m/z$ ，相对强度)232(${\mathrm{M}}^{ + },{21}$ )，217(78)，146(90)，133(100)，85(25)。

4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic Acid (4bd). ${}^{27}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 4bd (150mg,60%); yellow solid; mp 228-231 ${}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.11 (d, J = 8.0 Hz, 2H), 7.91 (d, J = 8.0 Hz, 2H), 1.37 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 172.2, 134.7, 133.8, 129.2, 84.3, 24.8; IR (film) 2981 (w), 1686 (m), 1360 (s), 1167 (w), 1143 (m), 1126 (m), 856 (m), 739 (w) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 248 (M*, 23), 233 (90), 162 (84), 149 (100), 148 (20), 85 (16).

4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯甲酸(4bd)。${}^{27}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1)得到4bd(150mg，60%)；黄色固体；熔点228 - 231${}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$ )δ8.11(d，J = 8.0Hz，2H)，7.91(d，J = 8.0Hz，2H)，1.37(s，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl3)δ172.2，134.7，133.8，129.2，84.3，24.8；红外光谱(薄膜)2981(弱)，1686(中)，1360(强)，1167(弱)，1143(中)，1126(中)，856(中)，739(弱)cm${}^{-1}$ ；电子轰击质谱(m/z，相对强度)248(M*，23)，233(90)，162(84)，149(100)，148(20)，85(16)。

Ethyl 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)- benzenesulfonate (4be). Flash column chromatography (silica gel, petroleum ether/EtOAc = 30:1 then 10:1) afforded 4be (240 mg, 77%); yellow solid; mp 82-84°C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta \; {7.98}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.89}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{4.12}(\mathrm{q}, J = {7.1}\mathrm{\;{Hz}}$ , 2H), ${1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{1.29}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 138.4,135.3,126.7,84.5,67.1,24.8,14.7; IR (film) 2981 (w), 1393 (m), 1358 (s), 1188 (m), 1143 (m), 1099 (w), 962 (w), 668 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS ( $m/z$ , relative intensity) 312 ( ${\mathrm{M}}^{ + },7$ ), 297 (52), 226 (100), 213 (27), 185 (18), 104 (18); HRMS (ESI) calcd for ${\mathrm{C}}_{14}{\mathrm{H}}_{22}{\mathrm{{BO}}}_{5}\mathrm{\;S}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 313.1278, found 313.1272.

4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯磺酸乙酯(4be)。快速柱色谱法(硅胶，石油醚/乙酸乙酯=30:1然后10:1)得到4be(240mg，77%)；黄色固体；熔点82 - 84°C。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta \; {7.98}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.89}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{4.12}(\mathrm{q}, J = {7.1}\mathrm{\;{Hz}}$ ，2H)，${1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{1.29}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 138.4，135.3，126.7，84.5，67.1，24.8，14.7；红外光谱(薄膜)2981(弱)，1393(中)，1358(强)，1188(中)，1143(中)，1099(弱)，962(弱)，668(中)${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱($m/z$ ，相对强度)312(${\mathrm{M}}^{ + },7$ )，297(52)，226(100)，213(27)，185(18)，104(18)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{14}{\mathrm{H}}_{22}{\mathrm{{BO}}}_{5}\mathrm{\;S}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 313.1278，实测值为313.1272。

(E)-1-Phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- phenyl)diazene (4bf). ${}^{22}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 200:1) afforded 4bf (184 mg, 60%); red solid; mp 87- ${89}^{ \circ }\mathrm{C}.{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.98-7.89 (m,6H),7.50-7.43 $\left( {\mathrm{m},3\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 154.3},{152.6}$ , 135.6, 131.1, 129.0, 122.9, 121.9, 84.0, 24.8; IR (film) 2978 (w), 1603 (w), 1397 (m), 1358 (s), 1142 (s), 1087 (s), 858 (m), 688 (m), 667 (w) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 308 $\left( {{\mathrm{M}}^{ + },{55}}\right) ,{203}\left( {100}\right)$ , 202 (24), 105 (32), 77 (84).

(E)-1-苯基-2-(4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)苯基)重氮烯(4bf)。${}^{22}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 200:1)得到4bf(184 mg，60%)；红色固体；熔点87 - ${89}^{ \circ }\mathrm{C}.{}^{1}\mathrm{H}$ 核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 7.98 - 7.89(m，6H)，7.50 - 7.43 $\left( {\mathrm{m},3\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振 $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 154.3},{152.6}$，135.6，131.1，129.0，122.9，121.9，84.0，24.8；红外光谱(薄膜)2978(w)，1603(w)，1397(m)，1358(s)，1142(s)，1087(s)，858(m), 688(m), 667(w)${\mathrm{{cm}}}^{-1}$；电子轰击质谱 $(m/z$，相对强度)308 $\left( {{\mathrm{M}}^{ + },{55}}\right) ,{203}\left( {100}\right)$，202(24)，105(32)，77(84)。

4,4,5,5-Tetramethyl-2-(4-vinylphenyl)-1,3,2-dioxaborolane (4bg). ${}^{23}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1 then 100:1) afforded 4bg (37 mg,16%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.77 (d, $J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.40 (d, $J = {7.8} \; \mathrm{{Hz}},2\mathrm{H}),{6.72}\left( {\mathrm{\;{dd}}, J = {10.9},{17.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.81}\left( {\mathrm{\;d}, J = {17.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${5.29}\left( {\mathrm{\;d}, J = {10.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 140.2, 136.9, 135.0, 125.5, 114.8, 83.8, 24.8; IR (film) 2979 (w), 1610 (w), 1398 (m), 1360 (s), 1144 (m), 1108 (w), 963 (w), 859 (m), 668 (m) c ${\mathrm{m}}^{-1}$ ; EI-MS (m/z, relative intensity) 230 (M ${}^{ + }$ , 52), 215 (40), 144 (82), 131 (90), 130 (100).

4,4,5,5-四甲基-2-(4-乙烯基苯基)-1,3,2-二氧硼杂环戊烷(4bg)。${}^{23}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 500:1 然后 100:1)得到4bg(37 mg，16%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400 MHz，CDCl ${}_{3}$)$\delta$ 7.77(d，$J = {7.8}\mathrm{\;{Hz}},2\mathrm{H}$)，7.40(d，$J = {7.8} \; \mathrm{{Hz}},2\mathrm{H}),{6.72}\left( {\mathrm{\;{dd}}, J = {10.9},{17.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.81}\left( {\mathrm{\;d}, J = {17.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，${5.29}\left( {\mathrm{\;d}, J = {10.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100 MHz，${\mathrm{{CDCl}}}_{3}$)δ 140.2，136.9，135.0，125.5，114.8，83.8，24.8；红外光谱(薄膜)2979(w)，1610(w)，1398(m)，1360(s)，1144(m)，1108(w)，963(w)，859(m)，668(m)c ${\mathrm{m}}^{-1}$；电子轰击质谱(m/z，相对强度)230(M ${}^{ + }$，52)，215(40)，144(82)，131(90)，130(100)。

4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (4bh). ${}^{20}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 25:1) afforded 4bh (135 mg, 62%); yellow solid; 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), 1.32 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 149.3, 136.4, 114.0, 83.2, 24.8; IR (film) 3450 (w), 3358 (w), 2927 (w), 1628 (w), 1359 (s), 1182 (w), 1143 (s), 860 (m), 738 (s) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) ${219}\left( {{\mathrm{M}}^{ + },{65}}\right) ,{204}\left( {16}\right) ,{161}\left( {13}\right) ,{133}\left( {22}\right) ,{120}$ (77), 119 (100).

4-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯胺(4bh)。${}^{20}$通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=25:1)得到4bh(135mg，62%)；黄色固体；熔点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)，1.32(s，12H)；${}^{13}\mathrm{C}$核磁共振(100MHz，CDCl${}_{3}$ )δ149.3，136.4，114.0，83.2，24.8；红外光谱(薄膜)3450(w)，3358(w)，2927(w)，1628(w)，1359(s)，1182(w)，1143(s)，860(m)，738(s)cm${}^{-1}$ ；电子轰击质谱(m/z，相对强度)${219}\left( {{\mathrm{M}}^{ + },{65}}\right) ,{204}\left( {16}\right) ,{161}\left( {13}\right) ,{133}\left( {22}\right) ,{120}$ (77)，119(100)。

1,4-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (4bi). ${}^{5a}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1 then 100:1) afforded 4bi (172 mg, 52%); pale yellow solid; mp ${232} - {233}{}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.81 (s,4H),1.34 (s, 24H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 133.8,83.8,24.8; IR (film) 2977 (w), 1439 (w), 1394 (m), 1371 (m), 1354 (s), 1142 (s), 1101 (s),858(s), 701 (w) ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity) 330 ( ${\mathrm{M}}^{ + }$ , 35), 315 (52), 273 (27), 244 (88), 231 (100), 230 (50), 131 (30).

1,4-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯(4bi)。${}^{5a}$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4bi(172mg，52%)；浅黄色固体；熔点${232} - {233}{}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 7.81(s，4H)，1.34(s，24H)；${}^{13}\mathrm{C}$核磁共振(100MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 133.8，83.8，24.8；红外光谱(薄膜)2977(w)，1439(w)，1394(m)，1371(m)，1354(s)，1142(s)，1101(s)，858(s)，701(w)${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(m/z，相对强度)330(${\mathrm{M}}^{ + }$ ，35)，315(52)，273(27)，244(88)，231(100)，230(50)，131(30)。

Triisopropyl((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- phenyl)ethynyl)silane (4bj. ${}^{24}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4bj (238 mg, 62%); orange solid; mp 80-82 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) 67.73 (d, J $= {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.46}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{1.13}\left( {\mathrm{\;s},{21}\mathrm{H}}\right)$ ; ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 134.4,131.1,126.2,107.2,92.0,83.9, 24.8, 18.6, 11.3; IR (film) 2943 (w), 2866 (w), 1606 (m), 1398 (m), 1358 (s), 1143 (m), 1019 (m), 860 (m), 675 (s) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 384 (M ${}^{ + }$ , 4), 342 (21), 341 (100), 313 (18), 299 (30), 285 (35), 271 (54), 185 (16), 171 (22).

三异丙基((4-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-苯基)乙炔基)硅烷(4bj)。${}^{24}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 500:1)得到4bj(238 mg，62%)；橙色固体；熔点80 - 82${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400 MHz，CDCl${}_{3}$ ) δ7.73(d，J$= {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.46}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{1.13}\left( {\mathrm{\;s},{21}\mathrm{H}}\right)$ ；${}^{13}\mathrm{C}$ 核磁共振碳谱(100 MHz，${\mathrm{{CDCl}}}_{3}$ ) δ134.4,131.1,126.2,107.2,92.0,83.9, 24.8, 18.6, 11.3；红外光谱(薄膜)2943(w)，2866(w)，1606(m)，1398(m)，1358(s)，1143(m)，1019(m)，860(m)，675(s) cm${}^{-1}$ ；电子轰击质谱(m/z，相对强度)384(M${}^{ + }$ ，4)，342(21)，341(百)，313(18)，299(30)，285(35)，271(54)，185(16)，171(22)。

2-(4-lodophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4bk). ${}^{7a}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4bk (132 mg,40%); pale yellow solid; mp 89-91 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.71 (d, $J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.51 (d, $J = \; {8.0}\mathrm{\;{Hz}},2\mathrm{H}),{1.33}$ (s,12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 136.9, 136.2, 98.8, 84.0, 24.8; IR (film) 2976 (w), 1587 (m), 1387 (m), 1359 (s), 1325 (m), 1088 (s), 1007 (m), 857 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 330 (M*, 100), 315 (52), 244 (82), 230 (71), 229 (76), 104 (35), 103 (30).

2-(4-碘苯基)-4,4,5,5-四甲基-1,3,2-二氧硼戊环(4bk)。${}^{7a}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 500:1)得到4bk(132 mg，40%)；浅黄色固体；熔点89 - 91${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(哈，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 7.71(d，$J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$ )，7.51(d，$J = \; {8.0}\mathrm{\;{Hz}},2\mathrm{H}),{1.33}$ (s，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100 MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 136.9, 136.2, 98.8, 84.0, 24.8；红外光谱(薄膜)2976(w)，1587(m)，1387(m)，1359(s)，1325(m)，1088(s)，1007(m)，857(m) cm${}^{-1}$ ；电子轰击质谱(m/z，相对强度)330(M*，百)百，315(52)，244(82)，230(71)，229(76)，104(35)，103(30)。

(E)-Ethyl 3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- phenyl)acrylate (4bl). ${}^{25}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 10:1) afforded 4bl (124 mg, 41%); Colorless oil. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 7.82 (d, $J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.69 (d, $J \; = {16.0}\mathrm{\;{Hz}},1\mathrm{H}),{7.52}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{6.49}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${4.26}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.36} - {1.34}\left( {\mathrm{m},{15}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $({100}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3})\delta$ 166.8,144.4,136.9,135.2,127.2,119.1,84.0,60.5,24.8, 14.3; IR (film) 2979 (w), 1714 (m), 1398 (m), 1359 (s), 1143 (s), 1089 (s), 858 (m), 706 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 302 $\left( {{\mathrm{M}}^{ + },{100}}\right) ,{287}\left( {72}\right) ,{257}\left( {22}\right) ,{216}\left( {60}\right) ,{203}\left( {92}\right) ,{157}\left( {64}\right) ,{129}$ (58), 77 (38).

(E)-3-(4-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯基)丙烯酸乙酯(4bl)。${}^{25}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1，然后10:1)得到4bl(124mg，41%)；无色油状物。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$)δ7.82(d，$J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}$)，7.69(d，$J \; = {16.0}\mathrm{\;{Hz}},1\mathrm{H}),{7.52}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{6.49}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，${4.26}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.36} - {1.34}\left( {\mathrm{m},{15}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$({100}\mathrm{{MHz}}$，${\mathrm{{CDCl}}}_{3})\delta$166.8，144.4，136.9，135.2，127.2，119.1，84.0，60.5，24.8，14.3；红外光谱(薄膜)2979(w)，1714(m)，1398(m)，1359(s)，1143(s)，1089(s)，858(m)，706(m)cm${}^{-1}$；电子轰击质谱(m/z，相对强度)302$\left( {{\mathrm{M}}^{ + },{100}}\right) ,{287}\left( {72}\right) ,{257}\left( {22}\right) ,{216}\left( {60}\right) ,{203}\left( {92}\right) ,{157}\left( {64}\right) ,{129}$(58)，77(38)。

2-(Biphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4bm). ${}^{26}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1 then 100:1) afforded 4bm (165 mg, 59%); yellow solid; mp 104-106 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.89 (d, $J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${7.61}\left( {\mathrm{\;d}, J = {7.1}\mathrm{\;{Hz}},4\mathrm{H}}\right) ,{7.43}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.35}(\mathrm{t}, J = {7.1}\mathrm{\;{Hz}}$ , 1H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 143.8, 141.0, 135.2, 128.7, 127.5, 127.2, 126.4, 83.8, 24.8; IR (film) 2978 (w), 1609 (w), 1398 (m), 1360 (s), 1144 (m), 1092 (m), 766 (m), 697 (m) ${\mathrm{{cm}}}^{-1}$ ; 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(4bm)。${}^{26}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1，然后100:1)得到4bm(165mg，59%)；黄色固体；熔点104 - 106 ${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 7.89(d，$J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}$ )，${7.61}\left( {\mathrm{\;d}, J = {7.1}\mathrm{\;{Hz}},4\mathrm{H}}\right) ,{7.43}\left( {\mathrm{t}, J = {7.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.35}(\mathrm{t}, J = {7.1}\mathrm{\;{Hz}}$ ，1H)，1.36(s，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl ${}_{3}$ )δ 143.8，141.0，135.2，128.7，127.5，127.2，126.4，83.8，24.8；红外光谱(薄膜)2978(w)，1609(w)，1398(m)，1360(s)，1144(m)，1092(m)，766(m)，697(m)${\mathrm{{cm}}}^{-1}$ ；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)。

2-(2-Isopropylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ca). ${}^{27}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4ca (118 mg,48%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.74 (d, $J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}$ ), 7.39-7.35 (m, 1H), 7.30 (d, $J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.15}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{3.68}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{1.23}(\mathrm{\;d}, J \; = {6.8}\mathrm{\;{Hz}},6\mathrm{H});{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 155.4,135.7,130.9, 124.8, 124.4, 83.3, 31.5, 24.8, 24.4; IR (film) 2976 (w), 1599 (w), 1380 (m), 1346 (s), 1310 (m), 1144 (s), 1060 (m), 861 (m), 766 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity) 246 (M ${}^{ + }$ , 20), 231 (15), 189 (50), 146 (56), 145 (60), 131 (74), 101 (62), 84 (100).

2-(2-异丙基苯基)-4,4,5,5-四甲基-1,3,2-二氧硼戊环(4ca)。${}^{27}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4ca(118mg，48%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400MHz，CDCl ${}_{3}$ ) $\delta$ 7.74(双峰，$J = {7.3}\mathrm{\;{Hz}},1\mathrm{H}$ )，7.39 - 7.35(多重峰，1H)，7.30(双峰，$J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}),{7.15}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{3.68}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ,{1.23}(\mathrm{\;d}, J \; = {6.8}\mathrm{\;{Hz}},6\mathrm{H});{}^{13}\mathrm{C}$ 核磁共振(100MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 155.4,135.7,130.9, 124.8, 124.4, 83.3, 31.5, 24.8, 24.4；红外光谱(薄膜)2976(弱)，1599(弱)，1380(中)，1346(强)，1310(中)，1144(强)，1060(中)，861(中)，766(中) ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(质荷比，相对强度)246(M ${}^{ + }$ ，20)，231(15)，189(50)，146(56)，145(60)，131(74)，101(62)，84(100)。

2-(2-Fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4cb). ${}^{7a}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4cb (108 mg,48%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) 67.76-7.72 (m, 1H), 7.42 (m, 1H), 7.13 (m, 1H), 7.02 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 167.2}(\mathrm{\;d}, J = \; {250.8}\mathrm{\;{Hz}}),{136.8}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}}}\right) ,{133.2}\left( {\mathrm{\;d}, J = {8.8}\mathrm{\;{Hz}}}\right) ,{123.5}(\mathrm{\;d}, J =$ 3.2 Hz), 115.2 (d, J = 23.8 Hz), 83.8, 24.8; IR (film) 2980 (w), 1615 (m), 1389 (m), 1356 (s), 1324 (m), 1144 (m), 1074 (m), 790 (w) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{222}\left( {{\mathrm{M}}^{ + },{23}}\right) ,{207}\left( {38}\right) ,{160}}\right)$ (19), 123 (100), 122 (33), 85 (18).

2-(2-氟苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷(4cb)。${}^{7a}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4cb(108mg，48%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$)δ7.76 - 7.72(多重峰，1H)，7.42(多重峰，1H)，7.13(多重峰，1H)，7.02$\left( {\mathrm{m},1\mathrm{H}}\right) ,{1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 167.2}(\mathrm{\;d}, J = \; {250.8}\mathrm{\;{Hz}}),{136.8}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}}}\right) ,{133.2}\left( {\mathrm{\;d}, J = {8.8}\mathrm{\;{Hz}}}\right) ,{123.5}(\mathrm{\;d}, J =$3.2Hz)，115.2(双峰，J = 23.8Hz)，83.8，24.8；红外光谱(薄膜)2980(弱)，1615(中)，1389(中)，1356(强)，1324(中)，1144(中)，1074(中)，790(弱)${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{222}\left( {{\mathrm{M}}^{ + },{23}}\right) ,{207}\left( {38}\right) ,{160}}\right)$(19)，123(100)，122(33)，85(18)。

2-(2-Chlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4cc). ${}^{28}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4cc (102 mg, 43%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.68 (d, $J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}$ ), 7.35-7.32 (m, 2H), 7.24- ${7.20}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 139.5}$ , 136.4, 131.8, 129.3, 125.8, 84.1, 24.7; IR (film) 2979 (w), 1593 (w), 1380 (m), 1352 (s), 1144 (s), 1039 (m), 758 (m), 670 (m) cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 240 (6),238 (M }{}^{ + }\text{ ,18),223 (21),203 }}\right)$ (100), 161 (44), 139 (90), 103 (20).

2-(2-氯苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷(4cc)。${}^{28}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4cc(102mg，43%)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$)$\delta$7.68(双峰，$J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}$)，7.35 - 7.32(多重峰，2H)，7.24 - ${7.20}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振氢谱$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 139.5}$，136.4，131.8，129.3，125.8，84.1，24.7；红外光谱(薄膜)2979(弱)，1593(弱)，1380(中)，1352(强)，1144(强)，1039(中)，758(中)，670(中)厘米${}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) 240 (6),238 (M }{}^{ + }\text{ ,18),223 (21),203 }}\right)$(100)，161(44)，139(90)，103(20)。

2-(2,6-Dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4cd). ${}^{19}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4 cd (53 mg, 23%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.11 (t, $J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}$ ), 6.93 (d, $J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}$ ), 2.39 (s, 6H), 1.38 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 141.7, 129.1, 126.4, 83.6, 24.9, 22.2; IR (film) 2978 (w), 1597 (w), 1371 (m), 1332 (s), 1302 (s), 1144 (s), 1060 (s), 859 (m), 770 (m) cm ${}^{-1}$ ; EI-MS (m/ $z$ , relative intensity) ${232}\left( {{\mathrm{M}}^{ + },{32}}\right) ,{175}\left( {100}\right) ,{174}\left( {35}\right) ,{133}\left( {53}\right) ,{132}$ (66).

2-(2,6-二甲基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环硼烷(4cd)。${}^{19}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4cd(53mg，23%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$) $\delta$ 7.11(t，$J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}$)，6.93(d，$J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}$)，2.39(s，6H)，1.38(s，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl${}_{3}$) δ 141.7，129.1，126.4，83.6，24.9，22.2；红外光谱(薄膜)2978(w)，1597(w)，1371(m)，1332(s)，1302(s)，1144(s)，1060(s)，859(m)，770(m)cm${}^{-1}$；电子轰击质谱(m/$z$，相对强度) ${232}\left( {{\mathrm{M}}^{ + },{32}}\right) ,{175}\left( {100}\right) ,{174}\left( {35}\right) ,{133}\left( {53}\right) ,{132}$ (66)。

2-(2-Methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ce). ${}^{29}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 100:1 then 50:1) afforded 4ce (61mg,26%); colorless liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl, ) 67.69-7.65 (m, 1H), 7.39 (m, 1H), 6.94 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{6.85}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.83}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 164.2, 136.7, 132.4, 120.2, 110.5, 83.4, 55.8, 24.8; IR (film) 2979 (w), 1600 (m), 1461 (m), 1386 (m), 1353 (s),1273 (m),1145 (m),1073 (m),760 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) ${234}\left( {{\mathrm{M}}^{ + },{67}}\right) ,{219}\left( {28}\right) ,{203}\left( {11}\right) ,{161}\left( {33}\right) ,{134}$ (100), 133 (60), 105 (47), 91 (69).

2-(2-甲氧基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环硼烷(4ce)。${}^{29}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1然后50:1)得到4ce(61mg，26%)；无色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl，) 67.69 - 7.65(m，1H)，7.39(m，1H)，6.94 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{6.85}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.83}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl3) δ 164.2，136.7，132.4，120.2，110.5，83.4，55.8，24.8；红外光谱(薄膜)2979(w)，1600(m)，1461(m)，1386(m)，1353(s)，1273(m)，1145(m)，1073(m)，760(m)cm${}^{-1}$；电子轰击质谱(m/z，相对强度) ${234}\left( {{\mathrm{M}}^{ + },{67}}\right) ,{219}\left( {28}\right) ,{203}\left( {11}\right) ,{161}\left( {33}\right) ,{134}$ (100)，133(60)，105(47)，91(69)。

2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (4cf). ${}^{30}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 100:1) afforded 4cf (44 mg, 20%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.80 (s,1H),7.61 (dd, $J = {1.6},{7.5}\mathrm{\;{Hz}},1\mathrm{H}$ ),7.37 (m,1H), ${6.90} - {6.86}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 163.6, 135.7, 133.8, 119.5, 115.4, 84.4, 24.8; IR (film) 3448 (w), 2980 (w), 1620 (s), 1486 (m), 1390 (s), 1167 (m), 1140 (s), 860 (m), 671 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity) 220 (M ${}^{ + }$ , 18), 163 (100), 162 (25), 121 (20), 120 (47).

2-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯酚(4cf)。${}^{30}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1)得到4cf(44mg，20%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.80(s，1H)，7.61(dd，$J = {1.6},{7.5}\mathrm{\;{Hz}},1\mathrm{H}$ )，7.37(m，1H)，${6.90} - {6.86}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 163.6，135.7，133.8，119.5，115.4，84.4，24.8；红外光谱(薄膜)3448(w)，2980(w)，1620(s)，1486(m)，1390(s)，1167(m)，1140(s)，860(m)，671(m) ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(m/z，相对强度)220(M ${}^{ + }$ ，18)，163(100)，162(25)，121(20)，120(47)。

2-(3-Fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4cg). ${}^{37}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4cg (104mg,47%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) 67.57 (d, J = 7.2 Hz, 1H), 7.48 (m, 1H), 7.33 (m, 1H), ${7.13}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 162.5 $\left( {\mathrm{d}, J = {246.4}\mathrm{\;{Hz}}}\right) ,{130.3}\left( {\mathrm{\;d}, J = {2.9}\mathrm{\;{Hz}}}\right) ,{129.4}\left( {\mathrm{\;d}, J = {7.0}\mathrm{\;{Hz}}}\right) ,{120.9} \; \left( {\mathrm{d}, J = {19.3}\mathrm{\;{Hz}}}\right) ,{118.1}\left( {\mathrm{\;d}, J = {21.0}\mathrm{\;{Hz}}}\right) ,{84.1},{24.8}$ ; IR (film) 2980 (w), 1431 (m), 1381 (m), 1355 (s), 1144 (m), 1091 (w), 901 (m), 716 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 222 (M ${}^{ + }$ , 39), 207 (85), 136 (98), 123 (100), 122 (37), 85 (18), 58 (18).

2-(3-氟苯基)-4,4,5,5-四甲基-1,3,2-二氧硼戊环(4cg)。${}^{37}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4cg(104mg，47%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl3) 67.57(d，J = 7.2Hz，1H)，7.48(m，1H)，7.33(m，1H)，${7.13}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.34}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，${\mathrm{{CDCl}}}_{3}$ ) δ 162.5 $\left( {\mathrm{d}, J = {246.4}\mathrm{\;{Hz}}}\right) ,{130.3}\left( {\mathrm{\;d}, J = {2.9}\mathrm{\;{Hz}}}\right) ,{129.4}\left( {\mathrm{\;d}, J = {7.0}\mathrm{\;{Hz}}}\right) ,{120.9} \; \left( {\mathrm{d}, J = {19.3}\mathrm{\;{Hz}}}\right) ,{118.1}\left( {\mathrm{\;d}, J = {21.0}\mathrm{\;{Hz}}}\right) ,{84.1},{24.8}$ ；红外光谱(薄膜)2980(w)，1431(m)，1381(m)，1355(s)，1144(m)，1091(w)，901(m)，716(m) ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 $(m/z$ ，相对强度)222(M ${}^{ + }$ ，39)，207(85)，136(98)，123(100)，122(37)，85(18)，58(18)。

2-(3-Bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ch). ${}^{32}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4ch (153 mg,54%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.93 (s, 1H), 7.71-7.56 (m, 2H), 7.22 (t, J = 7.7 Hz, 1H), 1.33 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 137.4, 134.1, 133.0, 129.4, 122.4, 84.1, 24.8; IR (film) 2979 (w), 1407 (m), 1372 (m), 1351 (s), 1321 (m), 1143 (s), 1101 (w), 700 (s) cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{284}\left( {43}\right) ,{282}\left( {{\mathrm{M}}^{ + },{51}}\right) ,{269}\left( {78}\right) ,{267}\left( {81}\right) }\right)$ , 198 (98), 196 (100), 185 (71), 183 (76), 103 (36), 85 (33).

2-(3-溴苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(4ch)。${}^{32}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4ch(153mg，54%);浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$) $\delta$ 7.93(s，1H)，7.71 - 7.56(m，2H)，7.22(t，J = 7.7Hz，1H)，1.33(s，12H); ${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl${}_{3}$) δ 137.4，134.1，133.0，129.4，122.4，84.1，24.8;红外光谱(薄膜)2979(w)，1407(m)，137(原文有误，应为1372)(m)，1351(s)，1321(m)，1143(s)，1101(w)，700(s)cm${}^{-1}$;电子轰击质谱$\left( {m/z\text{ , relative intensity) }{284}\left( {43}\right) ,{282}\left( {{\mathrm{M}}^{ + },{51}}\right) ,{269}\left( {78}\right) ,{267}\left( {81}\right) }\right)$，198(98)，196(100)，185(71)，183(76)，103(36)，85(33)。

2-(3-lodophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ci). ${}^{33}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4ci (132 mg,40%); yellow solid; mp 64-66 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl, δ 8.14 (s, 1H), 7.77-7.73 (m, 2H), 7.10 (t, $J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}),{1.33}$ (s,12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 143.4, 140.0, 133.6, 129.6, 94.5, 84.1, 24.8; IR (film) 2978 (w), 1402 (m), 1372 (m), 1349 (s), 1320 (m), 1143 (s), 1097 (w), 701 (m) cm ${}^{-1}$ ; EI-MS ( $m/z$ , relative intensity) 330 ( ${\mathrm{M}}^{ + }$ , 98), 315 (67), 244 (100), 231 (67), 230 (64), 104 (30), 103 (28).

2-(3-碘苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(4ci)。${}^{33}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到4ci(132mg，40%);黄色固体;熔点64 - 66${}^{ \circ }\mathrm{C}$。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl，δ 8.14(s，1H)，7.77 - 7.73(m，2H)，7.10(t，$J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}),{1.33}$(s，12H); ${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl${}_{3}$) $\delta$ 143.4，140.0，133.6，129.6，94.5，84.1，24.8;红外光谱(薄膜)2978(w) , 1402(m)，1372(m)，1349(s)，1320(m)，1143(s)，1097(w)，701(m)cm${}^{-1}$;电子轰击质谱($m/z$，相对强度)330(${\mathrm{M}}^{ + }$，98)，315(67)，244(100)，231(67)，230(64)，104(30)，103(28)。

3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (4cj). ${}^{29}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 30:1) afforded 4cj (147 mg,64%); colorless liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDC1, $\delta$ 8.09 (s, 1H), 8.01 (d, J = 7.5 Hz, 1H), 7.72-7.47 (m, 2H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl, ${}_{3}$ ) δ 138.6, 138.2, 134.2, 128.3, 118.7, 111.9, 84.4, 24.7; IR (film) 2980 (w), 2230 (w), 1603 (w), 1358 (s), 1167 (w), 1143 (s), 880 (m), 700 (s), 672 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{229}\left( {{\mathrm{M}}^{ + },{23}}\right) ,{214}\left( {96}\right) ,{186}}\right)$ (17), 143 (100), 130 (65), 58 (31).

3-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯甲腈(4cj)。${}^{29}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=30:1)得到4cj(147毫克，64%)；无色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫，CDCl，$\delta$ δ 8.09(单峰，1H)，8.01(双峰，J = 7.5赫兹，1H)，7.72 - 7.47(多重峰，2H)，1.36(单峰，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫，CDCl，${}_{3}$ ) δ 138.6，138.2，134.2，128.3，118.7，111.9，84.4，24.7；红外光谱(薄膜)2980(弱)，2230(弱)，1603(弱)，1358(强)，1167(弱)，1143(强)，880(中)，700(强)，672(中) ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity) }{229}\left( {{\mathrm{M}}^{ + },{23}}\right) ,{214}\left( {96}\right) ,{186}}\right)$ (17)，143(100)，130(65)，58(31)。

Ethyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (4ck). ${}^{18}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 30;1) afforded 4ck (192 mg,70%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 8.48 (s,1H),8.14 (d, $J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}$ ), 7.99-7.44 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{4.39}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.40}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right)$ , 1.35 $\left( {\mathrm{s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 166.5},{139.0},{135.6}$ , 132.2, 129.8, 127.6, 83.9, 60.8, 24.7, 14.3; IR (film) 2980 (w), 1720 (s), 1390 (m), 1358 (s), 1280 (m), 1252 (s), 1167 (m), 1144 (s), 734 (w), ${659}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${276}\left( {{\mathrm{M}}^{ + },{25}}\right) ,{261}$ (40), 233 (100), 205 (64), 177 (86), 149 (28), 131 (33), 103 (35).

3-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)苯甲酸乙酯(4ck)。${}^{18}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1，然后30:1)得到4ck(192毫克，70%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫兹，氘代氯仿${}_{3}$ ) $\delta$ δ8.48(单峰，1H)，8.14(双峰，$J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}$ )，7.99 - 7.44 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{4.39}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.40}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right)$ ，1.35 $\left( {\mathrm{s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振氢谱$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 166.5},{139.0},{135.6}$ ，132.2，129.8，127.6，83.9，60.8，24.7，14.3；红外光谱(薄膜)2980(弱)，1720(强)，1390(中)，1358(强)，1280(中)，1252(强)，1167(中)，1144(强)，734(弱)，${659}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$(m/z$ ，相对强度) ${276}\left( {{\mathrm{M}}^{ + },{25}}\right) ,{261}$ (40)，233(100)，205(64)，177(86)，149(28)，131(33)，103(35)。

4,4,5,5-Tetramethyl-2-m-tolyl-1,3,2-dioxaborolane (4cl). ${}^{34}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4cl (42 mg,19%); colorless solid; mp 33-34 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ 7.64-7.61 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.27}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{2.35}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}(\mathrm{\;s}$ , 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 137.0,135.3,132.0,131.8, 127.6, 83.6, 24.8, 21.2; IR (film) 2978 (w), 1379 (m), 1356 (s), 1145 (s), 1103 (w), 852 (m), 708 (s), 665 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 218 (M ${}^{ + }$ , 38), 203 (43), 132 (77), 119 (100), 118 (57), 91 (20).

4,4,5,5-四甲基-2-间甲苯基-1,3,2-二氧杂环戊硼烷(4cl)。${}^{34}$ 快速柱色谱法(硅胶,石油醚/乙酸乙酯=500:1)得到4cl(42mg,19%);无色固体;熔点33 - 34${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz,${\mathrm{{CDCl}}}_{3})\delta$ 7.64 - 7.61$\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.27}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{2.35}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}(\mathrm{\;s}$ ,12H);${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz,${\mathrm{{CDCl}}}_{3}$ )$\delta$ 137.0,135.3,132.0,131.8,127.6,83.6,24.8,21.2;红外光谱(薄膜)2978(w),1379(m),1356(s),1145(s),1103(w),852(m),708(s),665(m)cm${}^{-1}$ ;电子轰击质谱(m/z,相对强度)218(M${}^{ + }$ ,38),203(43),132(77),119(100),118(57),91(20)。

2-(3,5-Difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4cm). ${}^{35}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 4 cm ( ${151}\mathrm{{mg}}$ ,63%); colorless solid; yellow solid; mp ${36} - {38}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.28 (dd, $J = {1.9},{7.8}\mathrm{\;{Hz}}$ , 2H), 6.87 (tt, J = 2.4, 9.1 Hz, 1H), 1.34 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 162.7 (dd, $J = {11.0},{249.7}\mathrm{\;{Hz}}$ ), 116.8 (dd, $J = {5.7},{17.1}$ Hz), 106.5 (t, J = 25.1 Hz), 84.4, 24.8; IR (film); 2981 (w), 1587 (m), 1427 (s), 1368 (s), 1144 (m), 980 (m), 872 (m), 717 (w) cm ${}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) 240 $\left( {{\mathrm{M}}^{ + },{27}}\right) ,{225}\left( {81}\right) ,{197}\left( {10}\right) ,{154}$ (100), 141 (61), 85 (15), 58 (31).

2-(3,5-二氟苯基)-4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷(4cm)。${}^{35}$ 快速柱色谱法(硅胶,石油醚/乙酸乙酯=500:1)得到4cm(${151}\mathrm{{mg}}$,63%);无色固体;黄色固体;熔点${36} - {38}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz,${\mathrm{{CDCl}}}_{3}$ )$\delta$ 7.28(dd,$J = {1.9},{7.8}\mathrm{\;{Hz}}$,2H),6.87(tt, J = 2.4,9.1Hz,1H),1.34(s,12H);${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz, CDCl${}_{3}$ )$\delta$ 162.7(dd,$J = {11.0},{249.7}\mathrm{\;{Hz}}$),116.8(dd,$J = {5.7},{17.1}$Hz),106.5(t, J = 25.1Hz),84.4,24.8;红外光谱(薄膜);2981(w),1587(m),1427(s),1368(s),1144(m),980(m),872(m),717(w)cm${}^{-1}$ ;电子轰击质谱$\left( {m/z}\right.$,相对强度)240$\left( {{\mathrm{M}}^{ + },{27}}\right) ,{225}\left( {81}\right) ,{197}\left( {10}\right) ,{154}$(100),141(61),85(15),58(31)。

2-(3,4-Difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 4cn). ${}^{36}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1 then 100:1) afforded 4cn (156 mg, 65%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 7.60-7.51 (m, 2H), 7.17-7.10 (m, 1H), 1.34 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl, d 512.6 (dd, J = 12.7, 252.2 Hz), 150.2 (dd, J = 12.0, 248.6 Hz), 131.4 (dd, J = 3.8, 6.7 Hz), 123.3 (d, $J = {15.1}\mathrm{\;{Hz}}$ ), 116.9 (d, $J = {16.3}\mathrm{\;{Hz}}$ ), 84.2, 24.8; IR (film) 2981 (w), 1614 (m), 1519 (m), 1390 (s), 1360 (s), 1272 (s), 1167 (m),1144 (s), 890 (w), 689 (m) cm ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity) 240 (M*, 21), 225 (84), 154 (80), 141 (100), 131 (18), 79 (38), 58 (56).

2-(3,4-二氟苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷4cn)。${}^{36}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 500:1，然后100:1)得到4cn(156毫克，65%)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫兹，CDCl${}_{3}$)δ 7.60 - 7.51(多重峰，2H)，7.17 - 7.10(多重峰，1H)，1.34(单峰，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫兹，CDCl，d 512.6(双重峰，J = 12.7，252.2赫兹)，150.2(双重峰，J = 12.0，248.6赫兹)，131.4(双重峰，J = 3.8，6.7赫兹)，123.3(双峰，$J = {15.1}\mathrm{\;{Hz}}$)，116.9(双峰，$J = {16.3}\mathrm{\;{Hz}}$)，84.2，24.8；红外光谱(薄膜)2981(弱)，1614(中)，1519(中)，1390(强)，1360(强)，1272(强)，1167(中)，1144(强)，890(弱)，689(中)厘米${\mathrm{{cm}}}^{-1}$；电子轰击质谱(m/z，相对强度)240(M*，21)，225(84)，154(80)，141(百)，131(18)，79(38)，58(56)。

2-(Benzo[d][1,3]dioxol-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-lane (4co). ${}^{37}$ Flash chromatography (silica gel, petroleum ether/ EtOAc = 500:1) afforded 4co ( ${35}\mathrm{{mg}},{14}\%$ ); yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 7.36}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.24}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{6.83}(\mathrm{\;d}, J \; = {7.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.95}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}}}\right.$ , ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 150.2, 147.2, 129.7, 113.9, 108.3, 100.7, 83.7, 24.8; EI-MS $\left( {m/z\text{ , relative intensity) }{248}\left( {{\mathrm{M}}^{ + },{76}}\right) ,{233}\left( {20}\right) ,{162}\left( {43}\right) ,{149}({67}}\right)$ , 148 (100), 147 (50).

2-(苯并[d][1,3]二氧杂环戊烯-5-基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(4co)。${}^{37}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 500:1)得到4co(${35}\mathrm{{mg}},{14}\%$)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 7.36}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.24}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{6.83}(\mathrm{\;d}, J \; = {7.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.95}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}}}\right.$，${\mathrm{{CDCl}}}_{3}$)$\delta$ 150.2，147.2，129.7，113.9，108.3，100.7，83.7，24.8；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{248}\left( {{\mathrm{M}}^{ + },{76}}\right) ,{233}\left( {20}\right) ,{162}\left( {43}\right) ,{149}({67}}\right)$，148(百)，147(50)。

Dimethyl 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)- isophthalate (4cp). ${}^{38}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 4 cP (109 mg, 34%); yellow solid; mp ${125} - {127}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.76 (s,1H),8.64 (d, J = 1.4 Hz, 2H), 3.95 (s, 6H), 1.37 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 166.2,139.8,133.2,130.0,84.3,52.2,24.8; IR (film) 1726 (s), 1381 (m), 1334 (m), 1287 (m), 1262 (s), 1244 (s), 1008 (m), 736 (s) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 320 $\left( {{\mathrm{M}}^{ + },{11}}\right) ,{305}\left( {28}\right) ,{289}$ (25), 277 (100), 221 (55), 189 (24), 161 (22).

5-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)间苯二甲酸二甲酯(4cp)。${}^{38}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1)得到4cp(109mg，34%)；黄色固体；熔点${125} - {127}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$)δ8.76(s，1H)，8.64(d，J = 1.4Hz，2H)，3.95(s，6H)，1.37(s，12H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，${\mathrm{{CDCl}}}_{3}$) $\delta$ 166.2，139.8，133.2，130.0，84.3，52.2，24.8；红外光谱(薄膜)1726(s)，1381(m)，1334(m)，1287(m)，1262(s)，1244(s)，1008(m)，736(s) ${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)320 $\left( {{\mathrm{M}}^{ + },{11}}\right) ,{305}\left( {28}\right) ,{289}$(25)，277(100)，221(55)，189(24)，161(22)。

2-(4-Chloro-3-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-lane (4cq). ${}^{39}$ Flash column chromatography (silica gel, petroleum ether/EtOAc = 200:1) afforded 4cq (88 mg, 31%); yellow solid; mp 39-41 ${}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.24 (s, 1H), 7.89 (d, J = ${8.0}\mathrm{\;{Hz}},1\mathrm{H}),{7.54}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 147.8, 138.9, 131.3, 131.2, 129.5, 84.8, 24.8; IR (film) 2981 (w), 1604 (m), 1537 (m), 1390 (m), 1348 (s), 1143 (s), 1097 $\left( \mathrm{m}\right) ,{851}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${285}\left( 2\right) ,{283}\left( {{\mathrm{M}}^{ + }\text{ , }}\right.$ 7), 270 (30), 268 (90), 223 (26), 197 (40), 181 (80), 155 (100), 85 (42),58 (51); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{15}{\mathrm{\;B}}^{35}{\mathrm{{ClNNaO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$ 306.0677, found 306.0668.

2-(4-氯-3-硝基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(4cq)。${}^{39}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1)得到4cq(88mg，31%)；黄色固体；熔点39 - 41${}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$)δ8.24(s，1H)，7.89(d，J = ${8.0}\mathrm{\;{Hz}},1\mathrm{H}),{7.54}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.35}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl${}_{3}$)δ147.8，138.9，131.3，131.2，129.5，84.8，24.8；红外光谱(薄膜)2981(w)，1604(m)，1537(m)，1390(m)，1348(s)，1143(s)，1097 $\left( \mathrm{m}\right) ,{851}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度) ${285}\left( 2\right) ,{283}\left( {{\mathrm{M}}^{ + }\text{ , }}\right.$ 7)，270(30)，268(90)，223(26)，197(40)，181(80)，155(100)，85(42)，58(51)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{15}{\mathrm{\;B}}^{35}{\mathrm{{ClNNaO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{{Na}}\right\rbrack }^{ + }$ 306.0677，实测值为306.0668。

4,4,5,5-Tetramethyl-2-(naphthalen-2-yl)-1,3,2-dioxaborolane (5da). ${}^{40}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1) afforded 5da (58 mg, 23%); white solid; mp 64-66 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.42 (s, 1H), 7.89-7.82 (m, 4H), 7.49- ${7.47}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.39}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 136.2, 135.0, 132.8, 130.4, 128.6, 127.7, 126.9, 125.8, 83.9, 24.9; IR (film) 2978 (w), 1476 (m), 1383 (s), 1351 (s), 1144 (s), 1080 (m), 877 (m), 747 (s), 687 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 254 (M ${}^{ + }$ , 45), 239 (10), 168 (64), 154 (100), 128 (10).

4,4,5,5-四甲基-2-(萘-2-基)-1,3,2-二氧杂硼烷(5da)。${}^{40}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1)得到5da(58mg，23%)；白色固体；熔点64 - 66${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$ )δ8.42(s，1H)，7.89 - 7.82(m，4H)，7.49 - ${7.47}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.39}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl${}_{3}$ )δ136.2，135.0，132.8，130.4，128.6，127.7，126.9，125.8，83.9，24.9；红外光谱(薄膜)2978(w)，1476(m)，1383(s)，1351(s)，1144(s)，1080(m)，877(m)，747(s)，687(m)cm${}^{-1}$ ；电子轰击质谱(m/z，相对强度)254(M${}^{ + }$ ，45)，239(10)，168(64)，154(100)，128(10)。

2-Phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4H-chromen-4-one (5db). ${}^{41}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 15:1 then 10:1) afforded 5db (56 mg, 32%); yellow solid; mp 88-90 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.73 (d, $J = {1.2} \; \mathrm{{Hz}},1\mathrm{H}),{8.10}\left( {\mathrm{\;{dd}}, J = {1.4},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.94} - {7.92}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.56} - \; {7.52}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{6.85}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}({100}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}$ ) δ 178.4, 163.3, 158.2, 139.6, 133.3, 131.7, 131.6, 129.0, 126.3, 123.2, 117.3, 107.9, 84.2, 24.9; IR (film) 2978 (w), 2924 (w), 1644 (s), 1608 (m), 1351 (s), 1306 (m), 1143 (m), 712 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 348 (M ${}^{ + }$ , 73), 333 (44), 305 (39), 262 (20), 249 (100), 248 (71), 220 (19), 102 (54).

2-苯基-6-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-4H-色烯-4-酮(5db)。${}^{41}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=15:1然后10:1)得到5db(56mg，32%)；黄色固体；熔点88 - 90${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$ )δ8.73(d，$J = {1.2} \; \mathrm{{Hz}},1\mathrm{H}),{8.10}\left( {\mathrm{\;{dd}}, J = {1.4},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.94} - {7.92}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.56} - \; {7.52}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{6.85}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{1.37}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}({100}\mathrm{{MHz}}$ ，${\mathrm{{CDCl}}}_{3}$ )δ178.4，163.3，158.2，139.6，133.3，131.7，131.6，129.0，126.3，123.2，117.3，107.9，84.2，24.9；红外光谱(薄膜)2978(w)，2924(w)，1644(s)，1608(m)，1351(s)，1306(m)，1143(m)，712(m)cm${}^{-1}$ ；电子轰击质谱(m/z，相对强度)348(M${}^{ + }$ ，73)，333(44)，305(39)，262(20)，249(100)，248(71)，220(19)，102(54)。

6-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-chromen-2- one (5dc). Flash column chromatography (silica gel, petroleum ether/ EtOAc = 20:1 then 10:1) afforded 5dc (78 mg, 57%); white solid; mp ${105} - {107}{}^{ \circ }\mathrm{C}$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.96 $- {7.94}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ , ${7.72}\left( {\mathrm{\;d}, J = {9.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.32}\left( {\mathrm{\;d}, J = {8.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.42}(\mathrm{\;d}, J = {9.5}\mathrm{\;{Hz}}$ , 1H), ${1.36}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 160.6,156.1, 143.6, 138.1, 135.0, 118.3, 116.5, 116.2, 84.2, 24.8; IR (film) 2984 (w), 1753 (m), 1730 (s), 1393 (m), 1382 (s), 1371 (s), 1180 (m), 1131 (m) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 272 $\left( {{\mathrm{M}}^{ + },{71}}\right) ,{257}$ (69), 186 (100), 173 (96), 144 (58), 116 (20), 85 (15); HRMS (ESI) calcd for ${\mathrm{C}}_{15}{\mathrm{H}}_{18}{\mathrm{{BO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 273.1295, found 273.1291.

6-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-2H-色烯-2-酮(5dc)。快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到5dc(78mg，57%)；白色固体；熔点${105} - {107}{}^{ \circ }\mathrm{C}$；${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$7.96$- {7.94}\left( {\mathrm{\;m},2\mathrm{H}}\right)$，${7.72}\left( {\mathrm{\;d}, J = {9.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.32}\left( {\mathrm{\;d}, J = {8.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.42}(\mathrm{\;d}, J = {9.5}\mathrm{\;{Hz}}$，1H)，${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$160.6,156.1,143.6,138.1,135.0,118.3,116.5,116.2,84.2,24.8；红外光谱(薄膜)2984(w)，1753(m)，1730(s)，1393(m)，1,382(s)，1371(s)，1180(m)，1131(m)${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)272$\left( {{\mathrm{M}}^{ + },{71}}\right) ,{257}$(69)，186(100)，173(96)，144(58)，116(20)，85(15)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{15}{\mathrm{H}}_{18}{\mathrm{{BO}}}_{4}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$273.1295，实测值为273.1291。

3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (5dd). ${}^{19}$ Recrystallization from cyclohexane afforded 5dd (123 mg, 60%); white solid; mp 99-101 °C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.95 (s, 1H), ${8.69} - {8.65}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{8.06}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.30} - {7.27}(\mathrm{\;m}$ , 1H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl, δ 155.3, 151.8, 142.2, 123.0, 84.2, 24.8; IR (film) 2976 (w), 1474 (m), 1413 (m), 1363 (m), 1156 (s), 1048 (s), 1024 (m), 876 (m), 734 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 205 (M ${}^{ + }$ , 36), 190 (100), 148 (44), 120 (15), 106 (87), 105 (33).

3-(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)吡啶(5dd)。${}^{19}$从环己烷中重结晶得到5dd(123mg，60%)；白色固体；熔点99 - 101°C。${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$)δ8.95(s，1H)，${8.69} - {8.65}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{8.06}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.30} - {7.27}(\mathrm{\;m}$，1H)，1.36(s，12H)；${}^{13}\mathrm{C}$核磁共振(100MHz，CDCl，δ155.3，151.8，142.2，123.0，8 ~ 4.2，24.8；红外光谱(薄膜)2976(w)，1474(m)，1413(m)，1363(m)，1156(s)，1048(s)，1024(m)，876(m)，734(m)厘米${}^{-1}$；电子轰击质谱(m/z，相对强度)205(M${}^{ + }$，36)，190(100)，148(44)，120(15)，106(87)，105(33)。

5-Methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- thiophene-3-carbonitrile (5de). Flash column chromatography (silica gel, petroleum ether/EtOAc = 20:1) afforded 5de (37 mg, 15%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.05 (s,1H),2.52 (s, 3H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 147.9, 129.4, 117.9, 84.9, 24.7, 15.2; IR (film) 2926 (w), 2228 (w), 1726 (w), 1463 (s), 1364 (s), 1167 (m), 1140 (s), 1048 (s), 851 (s) cm ${}^{-1}$ ; EI-MS (m/ $z$ , relative intensity) ${249}\left( {{\mathrm{M}}^{ + },{62}}\right) ,{234}\left( {31}\right) ,{219}\left( {15}\right) ,{207}\left( {54}\right) ,{191}$ (54), 163 (28), 150 (100), 59 (30); HRMS (ESI) calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{17}{\mathrm{{BNO}}}_{2}\mathrm{\;S}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{250.1070}$ , found 250.1066.

5-甲基-2-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)噻吩-3-腈(5de)。通过快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1)得到5de(37mg，15%)；黄色液体。${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$) $\delta$ 7.05(s，1H)，2.52(s，3H)，1.36(s，12H)；${}^{13}\mathrm{C}$核磁共振(100MHz，CDCl${}_{3}$)δ147.9，129.4，117.9，84.9，24.7，15.2；红外(薄膜)2926(w)，2228(w)，1726(w)，1463(s)，1364(s)，1167(m)，1140(s)，1048(s)，851(s)cm${}^{-1}$；电子轰击质谱(m/$z$，相对强度)${249}\left( {{\mathrm{M}}^{ + },{62}}\right) ,{234}\left( {31}\right) ,{219}\left( {15}\right) ,{207}\left( {54}\right) ,{191}$(54)，163(28)，150(100)，59(30)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{17}{\mathrm{{BNO}}}_{2}\mathrm{\;S}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{250.1070}$，实测值为250.1066。

6-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (5df). ${}^{42}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 20:1 then 10:1) afforded 5df (53 pmg, 22%); orange solid; mp 181- ${183}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.22 (s, $1\mathrm{H}$ ),7.90 (s, $1\mathrm{H}$ ), ${7.65}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.56}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.24}(\mathrm{\;d}, J = {1.5}\mathrm{\;{Hz}}$ , 1H), 6.55 (s, 1H), 1.36 (s, 12H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) 6 135.5, 130.4, 125.6, 125.5, 120.0, 118.0, 102.7, 83.5, 24.9; IR (film) 3320 (w), 2925 (w), 1514 (m), 1392 (m), 1358 (s), 1166 (w), 1142 (s), ${894}\left( \mathrm{w}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) 243 $\left( {{\mathrm{M}}^{ + },{79}}\right) ,{228}$ (25), 170 (17), 157 (26), 144 (54), 143 (100), 116 (17).

6-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-1H-吲哚(5df)。${}^{42}$快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1，然后10:1)得到5df(53mg，22%)；橙色固体；熔点181-${183}^{ \circ }\mathrm{C}$。${}^{1}\mathrm{H}$核磁共振(400MHz，${\mathrm{{CDCl}}}_{3}$) $\delta$ 8.22(s，$1\mathrm{H}$)，7.9(b)，${7.65}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.56}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.24}(\mathrm{\;d}, J = {1.5}\mathrm{\;{Hz}}$，1H)，6.55(s，1H)，1.36(s，12H)；${}^{13}\mathrm{C}$核磁共振(100MHz，CDCl${}_{3}$)6 135.5，130.4，125.6，125.5，120.0，118.0，102.7., 83.5, 24.9；红外(薄膜)3320(w)，2925(w)，1514(m)，1392(m)，1358(s)，1166(w)，1142(s)，${894}\left( \mathrm{w}\right) {\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度)243$\left( {{\mathrm{M}}^{ + },{79}}\right) ,{228}$(25)，170(17)，157(26)，144(54)，143(100)，116(17)。

5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline (5dg). ${}^{43}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 10:1) afforded 5dg (143 mg, 56%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ 9.23 (s, 1H), 8.57 (s, 2H), 8.27 (d, J = 6.8 Hz, 1H), ${8.02}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.57}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.41}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 152.8, 143.5, 139.7, 139.4, 130.9, 128.3, 126.2, 121.0, 83.9, 24.8; IR (film) 2978 (w), 1612 (w), 1488 (w), 1371 (m), 1344 (s), 1136 (s), 1111 (w), 868 (m) cm ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity) 255 (M*, 63), 240 (20), 182 (18), 169 (40), 156 (55), 155 (100), 128 (19).

5-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)异喹啉(5dg)。${}^{43}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=10:1)得到5dg(143mg，56%)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl3)δ9.23(s，1H)，8.57(s，2H)，8.27(d，J = 6.8Hz，1H)，${8.02}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.57}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.41}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl${}_{3}$)δ152.8，143.5，139.7，139.4，130.9，128.3，126.2，121.0，83.9，24.8；红外光谱(薄膜)2978(w)，1612(w)，1488(w)，1371(m)，1344(s)，1136(s)，1111(w)，868(m)cm${\mathrm{{cm}}}^{-1}$；电子轰击质谱(m/z，相对强度)255(M*，63)，240(20)，182(18)，169(40)，156(55)，155(100)，128(19)。

2-Methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- pyridine (5di). ${}^{44}$ Flash chromatography (silica gel, petroleum ether/ EtOAc = 20:1) afforded 5di (117 mg,50%); yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.56}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.92}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.71}(\mathrm{\;d}, J \; = {8.3}\mathrm{\;{Hz}},1\mathrm{H}),{3.95}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 166.0,154.1,144.3,110.1,83.6,53.2,24.7; IR (film) 2979 (w), 1600 (s), 1500 (w), 1372 (m), 1354 (s), 1145 (m), 859 (m), 687 (w) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 235 $\left( {{\mathrm{M}}^{ + },{80}}\right) ,{234}\left( {100}\right)$ , 220 (19), 206 (15), 136 (88), 135 (63), 105 (28).

2-甲氧基-5-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)吡啶(5di)。${}^{44}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=20:1)得到5di(117mg，50%)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.56}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.92}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.71}(\mathrm{\;d}, J \; = {8.3}\mathrm{\;{Hz}},1\mathrm{H}),{3.95}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$166.0，154.1，144.3，110.1，83.6，53.2，24.7；红外光谱(薄膜)2979(w)，1600(s)，1500(w)，1372(m)，1354(s)，1145(m)，859(m)，687(w)${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)235$\left( {{\mathrm{M}}^{ + },{80}}\right) ,{234}\left( {100}\right)$，220(19)，206(15)，136(88)，135(63)，105(28)。

Borylation of 2-Naphthylamine (1da) in Water. 2-Naphthylamine (1da, 1 mmol, 143 mg), aqueous HCl (0.41 mL, 12 mol/L), and ${\mathrm{H}}_{2}\mathrm{O}\left( {{0.5}\mathrm{\;{mL}}}\right)$ were stirred with ice bath. Then, ${\mathrm{{NaNO}}}_{2}$ (1.1 mmol, ${76}\mathrm{{mg}}$ ) in ${\mathrm{H}}_{2}\mathrm{O}\left( {{0.5}\mathrm{\;{mL}}}\right)$ was added by dropping funnel. The reaction system was stirred for ${15}\mathrm{\;{min}}.{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}},{279}\mathrm{{mg}}}\right)$ and MeCN (1 mL) solution were then added in succession. The resulting solution was stirred at ${80}^{ \circ }\mathrm{C}$ for $2\mathrm{\;h}$ . The reaction mixture was then concentrated under reduced pressure, and the crude residue was purified by silica gel flash chromatography (petroleum ether). 4,4,5,5- Tetramethyl-2-(naphthalen-2-yl)-1,3,2-dioxaborolane (5da) was obtained (95 mg, 38%).

2-萘胺(1da)在水中的硼化反应。将2-萘胺(1da，1 mmol，143 mg)、盐酸水溶液(0.41 mL，12 mol/L)和${\mathrm{H}}_{2}\mathrm{O}\left( {{0.5}\mathrm{\;{mL}}}\right)$在冰浴中搅拌。然后，通过滴液漏斗加入${\mathrm{H}}_{2}\mathrm{O}\left( {{0.5}\mathrm{\;{mL}}}\right)$中含有的${\mathrm{{NaNO}}}_{2}$(1.1 mmol，${76}\mathrm{{mg}}$)。反应体系搅拌${15}\mathrm{\;{min}}.{\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}\left( {{1.1}\mathrm{{mmol}},{279}\mathrm{{mg}}}\right)$，然后依次加入乙腈(1 mL)溶液。所得溶液在${80}^{ \circ }\mathrm{C}$搅拌$2\mathrm{\;h}$。然后将反应混合物减压浓缩，粗残余物通过硅胶快速柱色谱法(石油醚)纯化。得到4,4,5,5-四甲基-2-(萘-2-基)-1,3,2-二氧杂硼烷(5da)(95 mg，38%)。

Typical Procedure of Consecutive Suzuki-Miyaura Cross-Coupling Reactions. ${\mathrm{B}}_{2}{\text{ pin }}_{2}$ (279 mg,1.1 mmol) and 3-amino-pyridine ( ${94}\mathrm{{mg}},{1.0}\mathrm{{mmol}}$ ) were weighed in a ${25}\mathrm{\;{mL}}$ round-bottom flask. MeCN ( $3\mathrm{\;{mL}}$ ) and $t$ -BuONO ( $2\mathrm{a},{155}\mathrm{{mg}},{1.5}\mathrm{{mmol}}$ ) were then added in succession. The resulting reaction solution was stirred for $2\mathrm{\;h}$ at ${80}^{ \circ }\mathrm{C}\left( {\mathrm{N}}_{2}\right.$ evolution completed within $5 - {15}\mathrm{\;{min}})$ . After the MeCN was removed by evaporation under reduced pressure, the system was degassed 3 times and was set under nitrogen atmosphere. Then $\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{58}\mathrm{{mg}},5\mathrm{{mmol}}\% }\right) ,{\mathrm{K}}_{2}{\mathrm{{CO}}}_{3}\left( {{276}\mathrm{{mg}},2\mathrm{{mmol}}}\right)$ , DMF $({1.5}$ mL), and PhI (245 mg, 1.2 mmol) were added, and the solution was stirred at ${100}^{ \circ }\mathrm{C}$ for ${12}\mathrm{\;h}$ . The solution was then concentrated by rotovap under reduced pressure to leave a crude residue, which was purified by silica gel column chromatography (petroleum ether/EtOAc $= {50} : 1$ , then 5:1) to give 3-phenylpyridine $6{\mathrm{f}}^{45}$ in ${63}\%$ isolated yield as pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.85 (s, $1\mathrm{H}$ ), 8.59 $\left( {\mathrm{d}, J = {4.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.86}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.57}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.47}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.42} - {7.33}\left( {\mathrm{\;m},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $({100}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.4,148.3,137.7,136.5,134.2,129.0,128.0,127.0,123.4; IR (film) 3031 (w), 1582 (w), 1473 (m), 1407 (m), 1024 (w), 1006 (w), 754 (s), 697 (s) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 155 (M ${}^{ + }$ , 100), 154 (50), 127 (14), 102 (10), 63 (8), 51 (13).

连续铃木-宫浦交叉偶联反应的典型步骤。${\mathrm{B}}_{2}{\text{ pin }}_{2}$(279毫克，1.1毫摩尔)和3-氨基吡啶(${94}\mathrm{{mg}},{1.0}\mathrm{{mmol}}$)称入一个${25}\mathrm{\;{mL}}$圆底烧瓶中。然后依次加入乙腈($3\mathrm{\;{mL}}$)和$t$-丁基亚硝酸酯($2\mathrm{a},{155}\mathrm{{mg}},{1.5}\mathrm{{mmol}}$)。所得反应溶液在$2\mathrm{\;h}$下搅拌，在${80}^{ \circ }\mathrm{C}\left( {\mathrm{N}}_{2}\right.$下反应，$5 - {15}\mathrm{\;{min}})$内反应完成。减压蒸发除去乙腈后，系统脱气3次并置于氮气气氛下。然后加入$\mathrm{{Pd}}{\left( {\mathrm{{PPh}}}_{3}\right) }_{4}\left( {{58}\mathrm{{mg}},5\mathrm{{mmol}}\% }\right) ,{\mathrm{K}}_{2}{\mathrm{{CO}}}_{3}\left( {{276}\mathrm{{mg}},2\mathrm{{mmol}}}\right)$、N, N-二甲基甲酰胺$({1.5}$毫升)和碘苯(245毫克，1.2毫摩尔)，溶液在${100}^{ \circ }\mathrm{C}$下搅拌${12}\mathrm{\;h}$。然后通过旋转蒸发仪减压浓缩溶液，得到粗残余物，通过硅胶柱色谱法(石油醚/乙酸乙酯$= {50} : 1$，然后5:1)纯化，得到3-苯基吡啶$6{\mathrm{f}}^{45}$，分离产率为${63}\%$，为浅黄色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$8.85(单峰，$1\mathrm{H}$)，8.59$\left( {\mathrm{d}, J = {4.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.86}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.57}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right)$，${7.47}\left( {\mathrm{t}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.42} - {7.33}\left( {\mathrm{\;m},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$({100}\mathrm{{MHz}}$，${\mathrm{{CDCl}}}_{3}$)$\delta$148.4、148.3、137.7、136.5、134.2、129.0、128.0、127.0、123.4；红外光谱(薄膜)3031(弱)，1582(弱)，1473(中)，1407(中)，1024(弱)，1006(弱)，754(强)，697(强)厘米${}^{-1}$；电子轰击质谱(m/z，相对强度)155(M${}^{ + }$，100))，154(50)，127(14)，102(10)，63(8)，5(13)。

4-Fluorobiphenyl (6a). ${}^{46}$ Flash chromatography (silica gel, petroleum ether) afforded 6a (122 mg, 71%); white solid; mp 75- ${77}^{ \circ }\mathrm{C}.{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.53-7.51 (m,4H),7.41 (t, $J = \; {7.2}\mathrm{\;{Hz}},2\mathrm{H}),{7.32}\left( {\mathrm{t}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.12} - {7.08}\left( {\mathrm{\;m},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 162.4}\left( {\mathrm{\;d}, J = {246.1}\mathrm{\;{Hz}}}\right) ,{140.2},{137.3}\left( {\mathrm{\;d}, J = {3.1}}\right) \; \mathrm{{Hz}}),{128.8},{128.6}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}}}\right) ,{127.2},{127.0},{115.6}\left( {\mathrm{\;d}, J = {21.4}\mathrm{\;{Hz}}}\right)$ ; IR (film) 1517 (m), 1485 (m), 1235 (m), 1196 (w), 907 (s), 837 (m), ${760}\left( \mathrm{\;m}\right) ,{732}\left( \mathrm{\;s}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) {172}\left( {{\mathrm{M}}^{ + },{100}}\right)$ , 171 (41), 170 (27), 142 (18), 100 (9), 85 (9).

4-氟联苯(6a)。${}^{46}$ 快速柱色谱法(硅胶，石油醚)得到6a(122毫克，产率71%)；白色固体；熔点75 - ${77}^{ \circ }\mathrm{C}.{}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta$ 7.53 - 7.51(多重峰，4个氢)，7.41(三重峰，$J = \; {7.2}\mathrm{\;{Hz}},2\mathrm{H}),{7.32}\left( {\mathrm{t}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.12} - {7.08}\left( {\mathrm{\;m},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振氢谱$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 162.4}\left( {\mathrm{\;d}, J = {246.1}\mathrm{\;{Hz}}}\right) ,{140.2},{137.3}\left( {\mathrm{\;d}, J = {3.1}}\right) \; \mathrm{{Hz}}),{128.8},{128.6}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}}}\right) ,{127.2},{127.0},{115.6}\left( {\mathrm{\;d}, J = {21.4}\mathrm{\;{Hz}}}\right)$ ；红外光谱(液膜)1517(中)，1485(中)，1235(中)，1196(弱)，907(强)，837(中)，${760}\left( \mathrm{\;m}\right) ,{732}\left( \mathrm{\;s}\right) {\mathrm{{cm}}}^{-1}$ ；电子轰击质谱$\left( {m/z\text{ , relative intensity }}\right) {172}\left( {{\mathrm{M}}^{ + },{100}}\right)$ ，171(相对丰度41)，170(27)，142(18)，100(9)，8(9)。

Biphenyl-4-carbonitrile (6b). ${}^{47}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 100:1) afforded 6b (88 mg, 49%); white solid; mp 83-85°C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 7.70 (m,4H), 7.59-7.42 (m, 5H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 145.6, 139.1, 132.5, 129.1, 128.6, 127.7, 127.2, 118.9, 110.8; IR (film) 2227 (m), 1606 (m), 1485 (m), 1265 (w), 1008 (w), 844 (m), 766 (s), 698 ${\mathrm{{cm}}}^{-1}$ ; EI-MS ( $m/z$ , relative intensity) 179 (M ${}^{ + }$ , 100), 178 (25), 151 (14), 76 (10), 63 (5).

联苯-4-甲腈(6b)。${}^{47}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 100:1)得到6b(88毫克，产率49%)；白色固体；熔点83 - 85°C。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫兹，${\mathrm{{CDCl}}}_{3}$ )δ 7.70(多重峰，4个氢)，7.59 - 7.42(多重峰，5个氢)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫兹，${\mathrm{{CDCl}}}_{3}$ )δ 145.6，139.1，132.5，129.1，128.6，127.7，127.2，118.9，110.8；红外光谱(液膜)2227(中)，1606(中)，1485(中)，1265(弱)，1008(弱)，844(中)，766(强)，698 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱($m/z$ ，相对丰度)179(M${}^{ + }$ ，100)，178(25)，151(14)，76(10)，63(5)。

Ethyl Biphenyl-3-carboxylate (6c). ${}^{48}$ Flash chromatography (silica gel, petroleum ether, then petroleum ether/EtOAc = 100:1) afforded 6c $\left( {{131}\mathrm{{mg}},{58}\% }\right)$ ; pale yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.28}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.02}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.75} - {7.61}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.50} - {7.42} \; \left( {\mathrm{m},3\mathrm{H}}\right) ,{7.35}\left( {\mathrm{t}, J = {7.3}\mathrm{{Hz}},1\mathrm{H}}\right) ,{4.40}\left( {\mathrm{q}, J = {7.2}\mathrm{{Hz}},2\mathrm{H}}\right) ,{1.40}(\mathrm{t}, J = \; {7.2}\mathrm{\;{Hz}},3\mathrm{H});{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 166.4,141.3,140.1, 131.3, 131.0, 128.8, 128.7, 128.2, 128.1, 127.6, 127.1, 61.0, 14.3; IR (film) 1717 (s), 1305 (m), 1272 (w), 1239 (s), 1108 (m), 1084 (w), ${742}\left( \mathrm{\;s}\right) ,{697}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) {226}\left( {{\mathrm{M}}^{ + },{73}}\right)$ , 198 (30), 181 (100), 153 (55), 152 (75), 76 (21).

联苯-3-羧酸乙酯(6c)。${}^{48}$ 快速柱色谱法(硅胶，石油醚，然后石油醚/乙酸乙酯 = 100:1)得到6c $\left( {{131}\mathrm{{mg}},{58}\% }\right)$ ；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振 $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.28}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.02}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.75} - {7.61}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.50} - {7.42} \; \left( {\mathrm{m},3\mathrm{H}}\right) ,{7.35}\left( {\mathrm{t}, J = {7.3}\mathrm{{Hz}},1\mathrm{H}}\right) ,{4.40}\left( {\mathrm{q}, J = {7.2}\mathrm{{Hz}},2\mathrm{H}}\right) ,{1.40}(\mathrm{t}, J = \; {7.2}\mathrm{\;{Hz}},3\mathrm{H});{}^{13}\mathrm{C}$ 核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 166.4,141.3,140.1, 131.3, 131.0, 128.8, 128.7, 128.2, 128.1, 127.6, 127.1, 61.0, 14.3；红外光谱(薄膜)1717(强)，1305(中)，1272(弱)，1239(强)，1108(中)，1084(弱)，${742}\left( \mathrm{\;s}\right) ,{697}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity }}\right) {226}\left( {{\mathrm{M}}^{ + },{73}}\right)$, 198 (30), 181 (100), 153 (55), 152 (75), 76 (21)。

(E)-Ethyl 3-(Biphenyl-4-yl)acrylate (6d). ${}^{49}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 200:1 then 100:1) afforded 6d (81mg, 32%); white solid; mp 77-79°C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.73 (d, $J = {16.0}\mathrm{\;{Hz}},1\mathrm{H}$ ),7.63-7.58 (m,6H),7.45-7.37 $\left( {\mathrm{m},3\mathrm{H}}\right) ,{6.47}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{4.28}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.35}(\mathrm{t}, J$ = 7.1 Hz, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 167.0, 144.1, 143.0, 140.2, 133.4, 128.9, 128.5, 127.8, 127.5, 127.0, 118.1, 60.5, 14.3; EI-MS $\left( {m/z\text{ , relative intensity) }{252}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{224}\left( {19}\right) ,{207}\left( {100}\right) ,{180}}\right)$ (46), 178 (78), 165 (32), 76 (20).

(E)-3-(联苯-4-基)丙烯酸乙酯(6d)。${}^{49}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=200:1，然后100:1)得到6d(81mg，32%)；白色固体；熔点77-79°C。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$)$\delta$ 7.73(d，$J = {16.0}\mathrm{\;{Hz}},1\mathrm{H}$)，7.63-至7.58(m，6H)，7.45-至7.37 $\left( {\mathrm{m},3\mathrm{H}}\right) ,{6.47}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{4.28}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.35}(\mathrm{t}, J$ =7.1Hz，3H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl ${}_{3}$)δ167.0，144.1，143.0，140.2，133.4，128.9，128.5，127.8，127.5，127.0，118.1，60.5，14.3；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{252}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{224}\left( {19}\right) ,{207}\left( {100}\right) ,{180}}\right)$ (46)，178(78)，165(32)，76(20)。

2,6-Diphenyl-4H-chromen-4-one (6e). ${}^{50}$ Flash column chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 20:1) afforded 6e $\left( {{122}\mathrm{{mg}},{41}\% }\right)$ ; white solid; mp 152-155°C; ${}^{1}\mathrm{H}$ NMR $({400}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.45 $\left( {\mathrm{d}, J = {2.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.96} - {7.93}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.69} - {7.63}(\mathrm{\;m}$ , 3H), 7.55-7.53 (m, 3H), 7.47 (t, J = 7.4 Hz, 2H), 7.39 (t, J = 7.4 Hz, 1H), 6.87 (s, 1H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 178.5, 163.4, 155.6, 139.2, 138.4, 132.6, 131.7, 131.6, 129.0, 128.9, 127.8, 127.1, 126.3, 124.0, 123.5, 118.6, 107.5; IR (film) 1634 (s), 1616 (s), 1496 (w), 1473 (m), 1359 (s), 1049 (w), 772 (m), 687 (m) cm ${}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{21}{\mathrm{H}}_{15}{\mathrm{O}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{299.1067}$ , found 299.1063.

2,6-二苯基-4H-色烯-4-酮(6e)。${}^{50}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1，然后20:1)得到6e $\left( {{122}\mathrm{{mg}},{41}\% }\right)$；白色固体；熔点152-155°C；${}^{1}\mathrm{H}$ 核磁共振氢谱$({400}\mathrm{{MHz}}$ ，${\mathrm{{CDCl}}}_{3}$)$\delta$ 8.45 $\left( {\mathrm{d}, J = {2.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.96} - {7.93}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.69} - {7.63}(\mathrm{\;m}$ ，3H)，7.55-至7.53(m，3H)，7.47(t，J =7.4Hz，2H)，7.39(t，J =7.4Hz，1H)，6.87(s，1H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl ${}_{3}$)δ178.5，163.4，155.6，139.2，138.4，132.6，131.7，131.6，129.0，128.9，127.8，127.1，126.3，124.0，123.5，118.6，107.5；红外光谱(薄膜)1634(s)，1616(s)，1496(w)，1473(m)，1359(s)，1049(w)，772(m)，687(m)cm ${}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{21}{\mathrm{H}}_{15}{\mathrm{O}}_{2}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{299.1067}$ ，实测值为299.1063。

2-Methyl-5-phenylpyridine (6g). ${}^{51}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 20:1 then 5:1) afforded 6g (91 mg, 54%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.73 (s,1H) ${7.75}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.55}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.45} - {7.20}\left( {\mathrm{\;m},4\mathrm{H}}\right)$ , 2.59 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 157.1, 147.4, 137.8, 134.6, 133.6, 128.9, 127.7, 126.8, 123.0, 24.0; IR (film) 1604 (w), 1479 (m),1445 (w),1374 (w),1030 (w),759 (s),731 (w),697 (s) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) }{169}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{168}\left( {24}\right) ,{141}\left( {23}\right) }\right)$ , 115 (18), 102 (10), 51 (8).

2-甲基-5-苯基吡啶(6g)。${}^{51}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 20:1 然后 5:1)得到 6g(91mg，54%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl${}_{3}$)δ 8.73(单峰，1H)${7.75}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.55}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.45} - {7.20}\left( {\mathrm{\;m},4\mathrm{H}}\right)$，2.59(单峰，3H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl${}_{3}$)δ 157.1，147.4，137.8，134.6，133.6，128.9，127.7，126.8，~123.0，24.0；红外光谱(薄膜)1604(弱)，1479(中)，1445(弱)，1374(弱)，1030(弱)，759(强)，731(弱)，697(强)${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity) }{169}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{168}\left( {24}\right) ,{141}\left( {23}\right) }\right)$，115(18)，102(10)，51(8)。

3-Methyl-5-phenylpyridine (6h). ${}^{52}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 5:1) afforded 6h ( ${59}\mathrm{{mg}}$ , 35%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ 8.66 (s, $1\mathrm{H}$ ), ${8.42}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.66}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.56} - {7.38}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{2.38}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 148.8, 145.4, 137.8, 136.0, 134.8, 132.9, 128.9, 127.8, 127.0, 18.3; IR (film) 3033 (w), 1453 (w), 1414 (m), 1150 (w), ${1028}\left( \mathrm{\;w}\right) ,{875}\left( \mathrm{\;m}\right) ,{760}\left( \mathrm{\;s}\right) ,{697}\left( \mathrm{\;s}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 169 (M ${}^{ + }$ , 100), 168 (35), 141 (15), 115 (16), 102 (6).

3-甲基-5-苯基吡啶(6h)。${}^{52}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 5:1)得到 6h(${59}\mathrm{{mg}}$，35%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，CDCl3)δ 8.66(单峰，$1\mathrm{H}$)，${8.42}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.66}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.56} - {7.38}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{2.38}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，CDCl3)δ 148.8，145.4，137.8，136.0，134.8，132.9，128.9，127.8，127.0，18.3；红外光谱(薄膜)3033(弱)，1453(弱)，1414(中)，1150(弱)，${1028}\left( \mathrm{\;w}\right) ,{875}\left( \mathrm{\;m}\right) ,{760}\left( \mathrm{\;s}\right) ,{697}\left( \mathrm{\;s}\right) {\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度)169(M${}^{ + }$，100)，168(35)，141(15)，115(16)，102(6)。

4-Methyl-3-phenylpyridine (6i). ${}^{52}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 5:1) afforded 6i (88 mg, 52%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.44 (s,2H),7.45-7.31 $\left( {\mathrm{m},5\mathrm{H}}\right) ,{7.18}\left( {\mathrm{\;d}, J = {2.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.28}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.9,148.2,144.4,137.8,137.6,129.2,128.3,127.5,125.1, 19.7; IR (film) 1590 (m), 1444 (m), 1401 (m), 1007 (m), 995 (w), 766 (s), 732 (w), 702 (s) cm ${}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 169 $\left( {{\mathrm{M}}^{ + },{95}}\right) ,{168}\left( {100}\right) ,{167}\left( {49}\right) ,{154}\left( {20}\right) ,{115}\left( {18}\right) ,{91}\left( {18}\right)$ .

4-甲基-3-苯基吡啶(6i)。${}^{52}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1，然后5:1)得到6i(88毫克，52%);黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.44(s，2H)，7.45 - 7.31 $\left( {\mathrm{m},5\mathrm{H}}\right) ,{7.18}\left( {\mathrm{\;d}, J = {2.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.28}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.9，148.2，144.4，137.8，137.6，129.2，128.3，127.5，125.1，19.7;红外光谱(薄膜)1590(m)，1444(m)，1401(m)，1007(m)，995(w)，766(s)，732(w)，702(s)厘米${}^{-1}$ ;电子轰击质谱$(m/z$ ，相对强度)169 $\left( {{\mathrm{M}}^{ + },{95}}\right) ,{168}\left( {100}\right) ,{167}\left( {49}\right) ,{154}\left( {20}\right) ,{115}\left( {18}\right) ,{91}\left( {18}\right)$ 。

Methyl 5-Phenylnicotinate (6j). ${}^{53}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 5:1) afforded 6j (106 mg, 50%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 9.19 (s, $1\mathrm{H}$ ),9.00 (s, 1H), 8.48 (s, 1H), 7.61-7.43 (m, 5H), 3.98 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDC1, 5 165.6, 151.7, 149.2, 136.5, 136.3, 135.1, 129.1, 128.5, 127.1, 125.9, 52.4; IR (film) 1726 (s), 1440 (m), 1310 (s), 1251 (s), ${1111}\left( \mathrm{\;m}\right) ,{1026}\left( \mathrm{w}\right) ,{754}\left( \mathrm{\;s}\right) ,{700}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) ${213}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{182}\left( {67}\right) ,{154}\left( {68}\right) ,{127}\left( {48}\right) ,{77}\left( {30}\right) ,{63}$ (9).

5-苯基烟酸甲酯(6j)。${}^{53}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1，然后5:1)得到6j(106毫克，50%);黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 9.19(s，$1\mathrm{H}$ )，9.00(s，1H) ,8.48(s，1H)，7.61 - 7.43(m，5H)，3.98(s，3H); ${}^{13}\mathrm{C}$ 核磁共振(100兆赫，CDCl₃)165.6，151.7，149.2，136.5，136.3，135.1，129.1，128.5，127.1，125.9，52.4;红外光谱(薄膜)1726(s)，1440(m)，1310(s)，1251(s)，${1111}\left( \mathrm{\;m}\right) ,{1026}\left( \mathrm{w}\right) ,{754}\left( \mathrm{\;s}\right) ,{700}\left( \mathrm{\;m}\right) {\mathrm{{cm}}}^{-1}$ ;电子轰击质谱$(m/z$ ，相对强度) ${213}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{182}\left( {67}\right) ,{154}\left( {68}\right) ,{127}\left( {48}\right) ,{77}\left( {30}\right) ,{63}$ (9)。

5-Phenyl-2-(trifluoromethyl)pyridine (6k). ${}^{54}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 100:1) afforded 6k (134 mg, 60%); white solid; mp 90-92°C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.80 $\left( {\mathrm{s},1\mathrm{H}}\right) ,{7.89}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.61}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.46}(\mathrm{\;d}, J = \; {7.4}\mathrm{\;{Hz}},2\mathrm{H}),{7.40} - {7.33}\left( {\mathrm{\;m},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.3, 146.6 (q, J = 34.7 Hz), 139.4, 136.2, 135.4, 129.2, 128.9, 127.2, 121.8 (q, J = 272 Hz), 120.3; IR (film) 1376 (w), 1339 (s), 1245 (m), 1174 (m), 1121 (s), 1093 (s), 1042 (w), 754 (m) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 223 (M ${}^{ + }$ , 100), 222 (21), 154 (25), 127 (20), 102 (10), 77 (10).

5-苯基-2-(三氟甲基)吡啶(6k)。${}^{54}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=100:1)得到6k(134mg，60%)；白色固体；熔点90 - 92°C。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz，${\mathrm{{CDCl}}}_{3}$ )δ8.80 $\left( {\mathrm{s},1\mathrm{H}}\right) ,{7.89}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.61}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.46}(\mathrm{\;d}, J = \; {7.4}\mathrm{\;{Hz}},2\mathrm{H}),{7.40} - {7.33}\left( {\mathrm{\;m},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 148.3, 146.6(q, J = 34.7Hz), 139.4, 136.2, 135.4, 129.2, 128.9, 127.2, 121.8(q, J = 272Hz), 120.3；红外光谱(薄膜)1376(w)，1339(s)，1245(m)，1174(m)，1121(s)，1093(s)，1042(w)，754(m)cm ${}^{-1}$ ；电子轰击质谱(m/z，相对强度)223(M ${}^{ + }$ ，100)，222(21)，154(25)，127(20)，102(10)，77(10)。

2-Methoxy-5-phenylpyridine (6I). ${}^{55}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1) afforded 61 (92 mg, 50%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl,3) $\delta$ 8.39 (s,1 H),7.77 (d, $J = {8.5} \; \mathrm{{Hz}},1\mathrm{H}),{7.51}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.43} - {7.34}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{6.81}(\mathrm{\;d}, J = {8.5}$ Hz, 1H), 3.98 (s, 3H); ${}^{13}$ C NMR (100 MHz, CDCl ${}_{3}$ ) δ 163.6, 144.9, 137.9, 137.4, 130.0, 128.9, 127.2, 126.6, 110.8, 53.5; IR (film) 1606 (m), 1508 (m), 1480 (s), 1286 (s), 1046 (w), 1019 (m), 830 (m), 769 (s) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity) 185 (M ${}^{ + }$ , 98), 184 (100), 156 (42), 154 (46), 128 (12), 115 (31).

2-甲氧基-5-苯基吡啶(6I)。${}^{55}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=50:1)得到61(92mg，50%)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz, CDCl₃) $\delta$ 8.39(s,1H),7.77(d, $J = {8.5} \; \mathrm{{Hz}},1\mathrm{H}),{7.51}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.43} - {7.34}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{6.81}(\mathrm{\;d}, J = {8.5}$ Hz,1H), 3.98(s, 3H)；${}^{13}$ 核磁共振碳谱(100MHz, CDCl ${}_{3}$ )δ163.6, 144.9, 137.9, 137.4, 130.0, 128.9, 127.2, 126.6, 110.8, 53.5；红外光谱(薄膜)1606(m)，1508(m)，1480(s) , 1286(s)，1046(w)，1019(m)，830(m)，769(s) ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 $(m/z$ ，相对强度)185(M ${}^{ + }$ ，98)，184(100)，156(42)，154(46)，128(12)，115(31)。

3-Bromo-5-phenylpyridine (6m). ${}^{56}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 5:1) afforded 6m (105 mg, 45%); white solid. mp 43-45 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.74 (s, 1H), 8.64 (s, 1H), 8.00 (s, 1H), 7.54-7.42 (m, 5H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 149.3, 146.3, 138.2, 136.8, 136.2, 129.1, 128.6, 127.1, 120.8; IR (film) 1580 (w), 1428 (m), 1405 (m), 1045 (w), 1011 (m), 798 (m), 760 (s), 698 (s) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 235 (98), 233 (M’, 100), 154 (32), 127 (71), 77 (28), 63 (22), 51 (18).

3-溴-5-苯基吡啶(6m)。${}^{56}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 5:1)得到 6m(105 毫克，45%)；白色固体。熔点 43 - 45 ${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400 兆赫兹，${\mathrm{{CDCl}}}_{3}$ )δ 8.74(单峰，1H)，8.64(单峰，1H)，8.00(单峰，1H)，7.54 - 7.42(多重峰，5H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100 兆赫兹，CDCl3)δ 149.3，146.3，138.2，136.8，136.2，129.1，128.6，127.1，120.8；红外光谱(薄膜)1580(弱)，1428(中)，1405(中)，1045(弱)，1011(中)，798(中)，760(强)，698(强)厘米 ${}^{-1}$ ；电子轰击质谱(质荷比，相对强度)235(98)，233(M’，100)，154(32)，127(71)，77(28)，63(22)，51(18)。

2-Chloro-4-phenylpyridine (6n). ${}^{57}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 10:1) afforded 6n (30 mg, 16%); pale yellow solid; mp 64-66 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {8.34}\left( {\mathrm{\;d}, J = {3.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.52}\left( {\mathrm{\;d}, J = {6.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.45}\left( {\mathrm{\;s},1\mathrm{H}}\right)$ , ${7.43} - {7.37}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.34}\left( {\mathrm{\;d}, J = {2.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 152.2, 151.5, 149.9, 136.8, 129.6, 129.2, 127.0, 122.0, 120.4; IR (film) 1604 (w), 1588 (s), 1535 (s), 1375 (m), 1130 (m), 878 (w), 760 (s), 730 (w) c ${\mathrm{m}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 191 (35), 189 }}\right) \; \left( {{\mathrm{M}}^{ + },{100}}\right) ,{154}\left( {57}\right) ,{127}\left( {36}\right) ,{77}\left( {14}\right) ,{51}\left( {10}\right)$ .

2-氯-4-苯基吡啶(6n)。${}^{57}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 10:1)得到 6n(30 毫克，16%)；浅黄色固体；熔点 64 - 66 ${}^{ \circ }\mathrm{C}$ 。${}^{1}\mathrm{H}$ 核磁共振氢谱(400 兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta = {8.34}\left( {\mathrm{\;d}, J = {3.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.52}\left( {\mathrm{\;d}, J = {6.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.45}\left( {\mathrm{\;s},1\mathrm{H}}\right)$ ，${7.43} - {7.37}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.34}\left( {\mathrm{\;d}, J = {2.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100 兆赫兹，CDCl ${}_{3}$ )δ 152.2，151.5，149.9，136.8，129.6，129.2，127.0，122.0，120.4；红外光谱(薄膜)1604(弱)，1588(强)，1535(强)，1375(中)，1130(中)，878(弱)，760(强)，730(弱)厘米 ${\mathrm{m}}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity) 191 (35), 189 }}\right) \; \left( {{\mathrm{M}}^{ + },{100}}\right) ,{154}\left( {57}\right) ,{127}\left( {36}\right) ,{77}\left( {14}\right) ,{51}\left( {10}\right)$ 。

3-Phenylquinoline (60). ${}^{58}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 10:1) afforded 6o (111 mg, 54%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 9.16 (s,1H) ${8.20}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.13}\left( {\mathrm{\;d}, J = {8.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.79}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.68} - \; {7.64}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.52} - {7.45}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.38}\left( {\mathrm{t}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 149.7, 147.1, 137.6, 133.6, 132.9, 129.2, 129.0, 129.0, 127.9, 127.8, 127.2, 126.8; IR (film) 3058 (w), 1597 (w), 1493 (m), 1362 (w), 1141 (w), 1025 (w), 786 (s), 761 (s), 696 (s) cm ${}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity) 205 (M ${}^{ + }$ , 100), 204 (58), 176 (14), 102 (9), 88 (8), 76 (11).

3-苯基喹啉(60)。${}^{58}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 10:1)得到 6o(111 mg，54%)；浅黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400 MHz，CDCl${}_{3}$)δ 9.16(单峰，1H)${8.20}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.13}\left( {\mathrm{\;d}, J = {8.5}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.79}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.68} - \; {7.64}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.52} - {7.45}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.38}\left( {\mathrm{t}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100 MHz，CDCl${}_{3}$)δ 149.7、147.1、137.6、133.6、132.9、129.2、129.0、129.0、127.9、127.8、127.2、126.8；红外光谱(薄膜)3058(弱)、1597(弱)、1493(中)、1362(弱)、1141(弱)、1025(弱)、786(强)、761(强)、696(强)cm${}^{-1}$；电子轰击质谱$\left( {m/z}\right.$(m/z，相对强度)205(M${}^{ + }$，100)、204(58)、176(14)、102(9)、88(8)、76(11)。

5-Phenylisoquinoline (6p). ${}^{59}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 5:1) afforded 6p (113 mg, 55%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 9.30 (s,1H),8.48 (d, $J = \; {5.7}\mathrm{\;{Hz}},1\mathrm{H}),{7.96}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.71}\left( {\mathrm{\;d}, J = {5.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.63}(\mathrm{\;d}, J = {4.1}\mathrm{\;{Hz}}$ , 2H), 7.52-7.43 (m, 5H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 152.8, 143.3, 139.1, 138.9, 134.0, 130.8, 129.8, 128.9, 128.4, 127.7, 127.0, 126.7, 118.4; IR (film) 3055 (w), 1618 (m), 1485 (m), 1058 (w), 829 (s),799 (w), 758 (s), 701 (s) cm ${}^{-1}$ ; EI-MS (m/z, relative intensity) 205 (M*, 100), 204 (76), 178 (19), 176 (30), 151 (13), 102 (18), 88(18).

5-苯基异喹啉(6p)。${}^{59}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 5:1)得到 6p(113 mg，55%)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400 MHz，CDCl${}_{3}$)δ 9.30(单峰，1H)，8.48(双峰，$J = \; {5.7}\mathrm{\;{Hz}},1\mathrm{H}),{7.96}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.71}\left( {\mathrm{\;d}, J = {5.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.63}(\mathrm{\;d}, J = {4.1}\mathrm{\;{Hz}}$，2H)，7.52 - 7.43(多重峰，5H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100 MHz，CDCl${}_{3}$)δ 152.8、143.3、139.1、138.9、134.0、130.8、129.8、128.9、128.4、127.7、127.0、126.7、118.4；红外光谱(薄膜)3055(弱)、1618(中)、1485(中)、1058(弱)、829(强)、799(弱)、758(强)、701(强)cm${}^{-1}$；电子轰击质谱(m/z，相对强度)205(M*，100)、204(76)、178(19)、176(30)、151(13)、102(18)、88(18)。

4-Phenylisoquinoline (6q). ${}^{60}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 5:1) afforded 6q (88 mg, 43%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 9.25 (s, $1\mathrm{H}$ ), 8.49 (s, 1H), ${8.01}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.90}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.64} - {7.59}(\mathrm{\;m}$ , 2H), 7.50-7.46 (m, 5H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 151.8, 142.7, 136.9, 134.1, 133.2, 130.4, 130.0, 128.5, 128.3, 127.8, 127.8, 127.0, 124.7; IR (film) 3030 (w), 1620 (w), 1504 (w), 1390 (m), 1219 (w),1073 (w), 828 (w), 760 (s), 703 (s) ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative }}\right)$ intensity) ${205}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{204}\left( {73}\right) ,{178}\left( {15}\right) ,{176}\left( {22}\right) ,{151}\left( 8\right) ,{102}$ (15), 88 (12), 76 (11).

4-苯基异喹啉(6q)。${}^{60}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 5:1)得到 6q(88 毫克，43%)；黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400 兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$ 9.25(单峰，$1\mathrm{H}$)，8.49(单峰，1H)，${8.01}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.90}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.64} - {7.59}(\mathrm{\;m}$，2H)，7.50 - 7.46(多重峰，5H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100 兆赫兹，CDCl${}_{3}$)δ 151.8，142.7，136.9，134.1，133.2，130.4，130.0，128.5，128.3，127.8，127.7，127.0，124.7；红外光谱(薄膜)3030(弱)，1620(弱)，1504(弱)，1390(中)，1219(弱)，1073(弱)，828(弱)，760(强)，703(强)${\mathrm{{cm}}}^{-1}$；电子轰击质谱 $\left( {m/z\text{ , relative }}\right)$ 强度)${205}\left( {{\mathrm{M}}^{ + },{100}}\right) ,{204}\left( {73}\right) ,{178}\left( {15}\right) ,{176}\left( {22}\right) ,{151}\left( 8\right) ,{102}$(15)，88(12)，76(11)。

3-Phenyl-1H-indazole (6r). ${}^{61}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 10:1) afforded 6r (58 mg, 30%); yellow solid; mp 92-94°C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 10.4 (br, $1\mathrm{H}),{7.98}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.93}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.46}(\mathrm{t}, J = {7.4} \; \mathrm{{Hz}},2\mathrm{H}),{7.38} - {7.34}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.18}\left( {\mathrm{\;d}, J = {6.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 145.9, 141.7, 133.5, 128.8, 128.1, 127.6, 126.8, 121.4, 121.2,121.0,110.0; EI-MS $(m/z$ , relative intensity) 194 $\left( {{\mathrm{M}}^{ + },{100}}\right)$ , 193 (22), 167 (14), 165 (12), 77 (16), 51 (12).

3-苯基-1H-吲唑(6r)。${}^{61}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 10:1)得到 6r(58 毫克，30%)；黄色固体；熔点 92 - 94°C。${}^{1}\mathrm{H}$ 核磁共振氢谱(400 兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$ 10.4(宽峰，$1\mathrm{H}),{7.98}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.93}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.46}(\mathrm{t}, J = {7.4} \; \mathrm{{Hz}},2\mathrm{H}),{7.38} - {7.34}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.18}\left( {\mathrm{\;d}, J = {6.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100 兆赫兹，CDCl3)δ 145.9，141.7，133.5，128.8，128.1，127.6，126.8，121.4，121.2，121.0，110.0；电子轰击质谱 $(m/z$，相对强度)194 $\left( {{\mathrm{M}}^{ + },{100}}\right)$，193(22)，167(14)，165(12)，77(16)，51(12)。

3-Phenyl-1H-pyrazole (6s). ${}^{61}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 50:1 then 10:1) afforded 6s (29 mg, 20%); colorless liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.76 (d, $J = {1.3}\mathrm{\;{Hz}}$ , $1\mathrm{H}),{7.74}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.61}\left( {\mathrm{\;d}, J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.41}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.33}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.61}\left( {\mathrm{\;d}, J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {100}\right)$ MHz, CDCl ${}_{3}$ ) δ 148.8, 133.2, 131.9, 128.8, 128.1, 125.8, 102.7; IR (film) 3213 (m), 2978 (w), 1370 (m), 1353 (w), 1155 (m), 1113 (m), ${757}\left( \mathrm{\;s}\right) ,{693}\left( \mathrm{\;s}\right) {\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) {144}\left( {{\mathrm{M}}^{ + },{100}}\right)$ , 143 (14), 117 (14), 115 (31), 89 (15), 77 (15), 51 (13).

3-苯基-1H-吡唑(6s)。${}^{61}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯 = 50:1 然后 10:1)得到 6s(29 毫克，20%)；无色液体。${}^{1}\mathrm{H}$ 核磁共振(400 兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$ 7.76(双峰，$J = {1.3}\mathrm{\;{Hz}}$，$1\mathrm{H}),{7.74}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.61}\left( {\mathrm{\;d}, J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.41}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right)$，${7.33}\left( {\mathrm{t}, J = {7.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.61}\left( {\mathrm{\;d}, J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {100}\right)$ 兆赫，CDCl${}_{3}$)δ 148.8，133.2，131.9，128.8，128.1，125.8，102.7；红外(薄膜)3213(中)，2978(弱)，1370(中)，1353(弱)，1155(中)，1113(中)，${757}\left( \mathrm{\;s}\right) ,{693}\left( \mathrm{\;s}\right) {\mathrm{{cm}}}^{-1}$；电子轰击质谱 $\left( {m/z\text{ , relative intensity }}\right) {144}\left( {{\mathrm{M}}^{ + },{100}}\right)$，143(14)，117(14)，115(31), 89(15)，77(15)，51(13)。

Typical Procedure of Gram-Scale Borylation. 4-Nitroaniline (1ai, 20 mmol, 2.76 g) and ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$ (5.334 g, 21 mmol) were weighed in a ${250}\mathrm{\;{mL}}$ round-bottom flask. MeCN (60 mL), and $t$ -BuONO (3.09 g, 30 mmol) were then added in succession. The resulting reaction solution was allowed to stir for ${12}\mathrm{\;h}$ at ${80}^{ \circ }\mathrm{C}$ (nitrogen gas evolution completed within $1\mathrm{\;h}$ ). The solution was then concentrated under reduced pressure and the crude residue was purified by silica gel flash chromatography (petroleum ether/EtOAc = 500:1) to give 4,4,5,5- tetramethyl-2-(4-nitrophenyl)-1,3,2-dioxaborolane (4ai) ${}^{11}$ (3.88 g, 78%).

克级硼化的典型步骤。将 4-硝基苯胺(1ai，20 毫摩尔，2.76 克)和 ${\mathrm{B}}_{2}{\mathrm{{pin}}}_{2}$(5.334 克，21 毫摩尔)称入一个 ${250}\mathrm{\;{mL}}$ 圆底烧瓶中。然后依次加入乙腈(60 毫升)和 $t$-丁基亚硝酸酯(3.09 克，30 毫摩尔)。使所得反应溶液在 ${12}\mathrm{\;h}$ 下于 ${80}^{ \circ }\mathrm{C}$ 搅拌(在 $1\mathrm{\;h}$ 内氮气释放完毕)。然后将溶液减压浓缩，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 4,4,5,5-四甲基-2-(4-硝基苯基)-1,3,2-二氧硼戊环(4ai)${}^{11}$(3.88 克，78%)。

2-(4-Methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4aj). ${}^{11}$ Flash chromatography (silica gel, petroleum ether/EtOAc = 500:1 then 100:1) afforded 4aj (3.302 g,71%). Colorless liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.75 (d, $J = {8.7}\mathrm{\;{Hz}},2\mathrm{H}$ ), 6.89 (d, $J = {8.7} \; \mathrm{{Hz}},2\mathrm{H}),{3.82}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 162.1, 136.4, 113.2, 83.5, 55.0, 24.8; IR (film) 2978 (w), 1605 (s), 1396 (m), 1360 (s), 1318 (m), 1277 (m), 1247 (s), 1175 (w), 1143 (s), 1091 (m), 1031 (m), 962 (w), 860 (m), 831 (m), 736 (w) cm ${}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity) 234 }\left( {{\mathrm{M}}^{ + },{62}}\right) ,{219}\left( {27}\right) ,{148}\left( {39}\right) ,{135}}\right)$ (86), 134 (100), 133 (22), 43 (30), 41 (33).

2-(4-甲氧基苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(4aj)。${}^{11}$ 快速柱色谱法(硅胶，石油醚/乙酸乙酯=500:1然后100:1)得到4aj(3.302 g，71%)。无色液体。${}^{1}\mathrm{H}$ 核磁共振(400 MHz，CDCl ${}_{3}$ ) $\delta$ 7.75(双峰，$J = {8.7}\mathrm{\;{Hz}},2\mathrm{H}$ )，6.89(双峰，$J = {8.7} \; \mathrm{{Hz}},2\mathrm{H}),{3.82}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.33}\left( {\mathrm{\;s},{12}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100 MHz，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 162.1，136.4，113.2，83.5，55.0，24.8；红外光谱(薄膜)2978(弱)，1605(强)，1396(中)，1360(强)，1318(中)，1277(中)，1247(强)，1175(弱)，1143(强)，1091(中)，1031(中)，962(弱)，860(中)，831(中)，736(弱)厘米${}^{-1}$ ；电子轰击质谱$\left( {m/z\text{ , relative intensity) 234 }\left( {{\mathrm{M}}^{ + },{62}}\right) ,{219}\left( {27}\right) ,{148}\left( {39}\right) ,{135}}\right)$ (86)，134(100)，133(22)，43(30)，41(33)。

ASSOCIATED CONTENT

相关内容

S Supporting Information

S 支持信息

EPR experiments, 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.

EPR实验，所有产品的${}^{1}\mathrm{H}$和${}^{13}\mathrm{C}$光谱副本。该材料可通过互联网免费获取，网址为http://pubs.acs.org。

B AUTHOR INFORMATION

B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

The project is supported by National Basic Research Program (973 Program, No. 2012CB821600), Natural Science Foundation of China.

本项目受国家重点基础研究发展计划(973计划，编号:2012CB821600)、国家自然科学基金资助。

DEDICATION

献辞

Dedicated to the memory of Prof. Howard E. Zimmerman.

谨以此文纪念霍华德·E·齐默尔曼教授。

REFERENCES

参考文献

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