Cu(I)-Catalyzed Asymmetric Cross-Coupling of N-Tosylhydrazones and Trialkylsilylethynes: Enantioselective Construction of C(sp)-C(sp3) Bonds

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

Wen-Dao Chu, ${}^{a, b}$ Fangfang Guo, ${}^{b}$ Lefei Yu, ${}^{b}$ Junting Hong, ${}^{b}$ Qianyi Liu, ${}^{b}$ Fanyang Mo, ${}^{b}$ Yan Zhang ${}^{b}$ and Jianbo Wang*, b

朱文道，${}^{a, b}$ 郭芳芳，${}^{b}$ 余乐飞，${}^{b}$ 洪钧婷，${}^{b}$ 刘谦益，${}^{b}$ 莫凡洋，${}^{b}$ 张燕 ${}^{b}$ 及王剑波*，b

${}^{a}$ Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry &Chemical Engineering, China West Normal University, Nanchong 637002 (China)

${}^{a}$ 四川省化学合成与污染控制重点实验室，西华师范大学化学化工学院，南充637002(中国)

${}^{b}$ Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 (China)

${}^{b}$ 北京分子科学国家实验室(BNLMS)及教育部生物有机化学与分子工程重点实验室，北京大学化学学院，北京100871(中国)

The first catalytic enantioselective C(sp)-C(sp ${}^{3}$ ) cross-coupling reaction between $N$ -tosylhydrazones and trialkylsi-lylethynes in the presence of $\mathrm{{Cu}}\left( \mathrm{I}\right)$ salts and chiral phosphoramidite ligands was developed. A series of synthetically interesting, functionalized alkynes were obtained with moderate to good enantioselectivities (up to 83% ee). Cu(II) carbene migratory insertion is proposed to be the enantio-determining step.

首次开发了在$\mathrm{{Cu}}\left( \mathrm{I}\right)$盐和手性亚磷酰胺配体存在下，$N$-甲苯磺酰腙与三烷基硅乙炔之间的首例催化对映选择性C(sp)-C(sp${}^{3}$)交叉偶联反应。以中等至良好的对映选择性(高达83% ee)获得了一系列具有合成意义的官能化炔烃。提出Cu(II)卡宾迁移插入是对映体决定步骤。

Keywords C(sp)-C(sp ${}^{3}$ ) cross-coupling, metal carbene, asymmetric catalysis, Cu(I) catalysts, $N$ -tosylhydrazones

关键词 C(sp)-C(sp ${}^{3}$ )交叉偶联，金属卡宾，不对称催化，铜(I)催化剂，$N$ -对甲苯磺酰腙

Introduction

引言

Alkynes are versatile intermediates in the syntheses of natural products, biologically active molecules, and functional materials. ${}^{\left\lbrack 1\right\rbrack }$ Sonogashira coupling is a classical and powerful method for the synthesis of alkynes containing aryl $\mathrm{C}\left( {\mathrm{{sp}}}^{2}\right) - \mathrm{C}\left( \mathrm{{sp}}\right)$ bonds. ${}^{\left\lbrack 2\right\rbrack }$ However, it has been a challenge to construct alkyl $\mathrm{C}\left( {\mathrm{{sp}}}^{3}\right) - \mathrm{C}\left( \mathrm{{sp}}\right)$ bonds because of competing oxidative addition and $\beta$ -hydride elimination process. Significant progress has been made in this area in the last decade. Fu and co-workers reported the Sonogashira coupling of primary alkyl halides by employing a palladium/ $N$ -heterocyclic carbene catalyst system. ${}^{\left\lbrack 3\right\rbrack }$ Other groups have also developed efficient catalytic systems. ${}^{\left\lbrack 4\right\rbrack }$ Recently novel coupling reactions toward C(sp)-C(s ${\mathrm{p}}^{3}$ ) bond formation have also been extensively explored, such as radical-mediated alkylation, ${}^{\left\lbrack 5\right\rbrack }$ oxidative coupling, ${}^{\left\lbrack 6\right\rbrack }$ inter- or intramolecular decarboxylative cross-coupling ${}^{\left\lbrack 7\right\rbrack }$ and those involving organometallic reagents. ${}^{\left\lbrack 8\right\rbrack }$

炔烃是天然产物、生物活性分子和功能材料合成中的通用中间体。${}^{\left\lbrack 1\right\rbrack }$ Sonogashira偶联是合成含芳基$\mathrm{C}\left( {\mathrm{{sp}}}^{2}\right) - \mathrm{C}\left( \mathrm{{sp}}\right)$键的炔烃的经典且强大的方法。${}^{\left\lbrack 2\right\rbrack }$ 然而，由于竞争性氧化加成和$\beta$-氢化物消除过程，构建烷基$\mathrm{C}\left( {\mathrm{{sp}}}^{3}\right) - \mathrm{C}\left( \mathrm{{sp}}\right)$键一直是一个挑战。在过去十年中，该领域取得了重大进展。傅和他的同事报道了使用钯/$N$-杂环卡宾催化剂体系实现伯烷基卤化物的Sonogashira偶联。${}^{\left\lbrack 3\right\rbrack }$ 其他研究小组也开发了高效的催化体系。${}^{\left\lbrack 4\right\rbrack }$ 最近，针对C(sp)-C(s${\mathrm{p}}^{3}$)键形成的新型偶联反应也得到了广泛探索，如自由基介导的烷基化、${}^{\left\lbrack 5\right\rbrack }$ 氧化偶联、${}^{\left\lbrack 6\right\rbrack }$ 分子间或分子内脱羧交叉偶联${}^{\left\lbrack 7\right\rbrack }$ 以及涉及有机金属试剂的反应。${}^{\left\lbrack 8\right\rbrack }$

Regardless of the significant progress, only few examples of catalytic asymmetric $\mathrm{C}\left( {\mathrm{{sp}}}^{3}\right) - \mathrm{C}\left( \mathrm{{sp}}\right)$ bond formation have been reported. ${}^{\left\lbrack 9\right\rbrack }$ The groups of Sarandeses ${}^{\left\lbrack {10}\mathrm{a}\right\rbrack }$ and ${\mathrm{{Zhou}}}^{\left\lbrack {10}\mathrm{\;b}\right\rbrack }$ independently reported nickel-catalyzed enantioselective cross-coupling reactions between racemic secondary benzyl bromides and trialkynylindium or alkynylaluminum reagents. Recently, Sigman and coworkers developed an enantioselec-tive redox-relay Heck alkynylation of alkenols to conformation. However, the catalytic asymmetric version of the reaction has so far not been achieved. Therefore, it is of great significance to develop an asymmetric catalytic methodology for the asymmetric synthesis of $\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$ bond with this novel carbene coupling method. Herein, we report the first catalytic asymmetric $\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$ cross-coupling reaction between $N$ -tosylhydrazones and trialkylsilylethynes in the presence of $\mathrm{{Cu}}\left( \mathrm{I}\right)$ salts and chiral phosphoramidite ligands (Scheme 1b).

尽管取得了重大进展，但催化不对称$\mathrm{C}\left( {\mathrm{{sp}}}^{3}\right) - \mathrm{C}\left( \mathrm{{sp}}\right)$键形成的例子报道很少。${}^{\left\lbrack 9\right\rbrack }$ 萨兰德斯${}^{\left\lbrack {10}\mathrm{a}\right\rbrack }$和${\mathrm{{Zhou}}}^{\left\lbrack {10}\mathrm{\;b}\right\rbrack }$的研究小组分别报道了镍催化的外消旋仲苄基溴与三炔基铟或炔基铝试剂之间的对映选择性交叉偶联反应。最近，西格曼及其同事开发了烯醇的对映选择性氧化还原接力Heck炔基化反应以形成构象。然而，该反应的催化不对称版本迄今尚未实现。因此，开发一种不对称催化方法，通过这种新型卡宾偶联方法不对称合成$\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$键具有重要意义。在此，我们报道了在$\mathrm{{Cu}}\left( \mathrm{I}\right)$盐和手性亚磷酰胺配体存在下，$N$-甲苯磺酰腙与三烷基甲硅烷基乙炔之间的首次催化不对称$\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$交叉偶联反应(方案1b)。

Scheme 1 Cross-coupling of $N$ -tosylhydrazone with terminal alkyne

方案1 $N$-甲苯磺酰腙与末端炔烃的交叉偶联

a) our previous work (ref. 12)

a) 我们之前的工作(参考文献12)

struct $\beta$ -alkynyl carbonyl compounds in the presence of a Pd(II)/chiral pyridine oxazoline complex. ${}^{\left\lbrack {11}\right\rbrack }$

在Pd(II)/手性吡啶恶唑啉配合物存在下构建$\beta$-炔基羰基化合物。${}^{\left\lbrack {11}\right\rbrack }$

We have recently developed a straightforward method for the formation of $\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$ bonds starting from $N$ -tosylhydrazones and trialkylsilylethynes, with CuI as the catalyst (Scheme 1a). ${}^{\left\lbrack {12},{13}\right\rbrack }$ The reaction proceeds through carbene formation and migratory insertion. ${}^{\left\lbrack {14}\right\rbrack }$ These coupling reactions represent a highly efficient and practical approach for $\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$ bond

我们最近开发了一种直接的方法，以CuI作为催化剂，从$N$-对甲苯磺酰腙和三烷基硅乙炔出发形成$\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$键(方案1a)。${}^{\left\lbrack {12},{13}\right\rbrack }$该反应通过卡宾的形成和迁移插入进行。${}^{\left\lbrack {14}\right\rbrack }$这些偶联反应代表了一种用于形成$\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$键的高效且实用的方法

This article has been accepted for publication and undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record. Please cite this article as doi: 10.1002/cjoc.201700633

本文已被接受发表并经过全面同行评审，但尚未经过编辑、排版、分页和校对过程，这可能导致本版本与记录版本之间存在差异。请将本文引用为doi: 10.1002/cjoc.201700633

Experimental

实验

General

一般情况

All the reactions were performed under nitrogen atmosphere in a ${10}\mathrm{\;{mL}}$ Schlenk tube. All solvents were distilled prior to use. Dioxane was dried over ${\mathrm{{CaH}}}_{2}$ . For chromatography, 200-300 mesh silica gel (Qingdao, China) was employed. ${}^{1}\mathrm{H}$ NMR and ${}^{13}\mathrm{C}$ NMR spectra were recorded on Brucker ARX 400 spectrometer in ${\mathrm{{CDCl}}}_{3}$ solution and the chemical shifts were reported in parts per million (δ) relative to internal standard TMS (0 ppm). IR spectra were recorded on Nicolet iS10 in wave numbers, ${\mathrm{{cm}}}^{-1}$ . For HRMS measurements, the mass analyzer is FT-ICR. Optical rotations were measured at PerkinElmer Model 341LC Polarimeter and concentrations (c) were reported in $\mathrm{g} \times {\left( {100}\mathrm{\;{mL}}\right) }^{-1}$ . HPLC analysis was performed at Agilent Technologies 1200 apparatus with Chiracel column. Ligand 4a-b and 4e-h were purchased from DAICEL CHIRAL TECHNOLOGIES (CHINA) CO. LTD. Ligand $4\mathrm{c}$ and $4\mathbf{d}$ were synthesized by following the literatures. ${}^{\left\lbrack {15},{16}\right\rbrack }$

所有反应均在氮气气氛下于${10}\mathrm{\;{mL}}$史莱克管中进行。所有溶剂在使用前均进行蒸馏。二氧六环用${\mathrm{{CaH}}}_{2}$干燥。柱色谱使用200 - 300目硅胶(中国青岛)。${}^{1}\mathrm{H}$核磁共振和${}^{13}\mathrm{C}$核磁共振谱在布鲁克ARX 400光谱仪上于${\mathrm{{CDCl}}}_{3}$溶液中记录，化学位移以相对于内标TMS(0 ppm)的百万分之一(δ)报告。红外光谱在Nicolet iS10上以波数${\mathrm{{cm}}}^{-1}$记录。高分辨质谱测量中，质量分析器为傅里叶变换离子回旋共振。旋光度在珀金埃尔默341LC旋光仪上测量，浓度(c)以$\mathrm{g} \times {\left( {100}\mathrm{\;{mL}}\right) }^{-1}$报告。高效液相色谱分析在安捷伦科技1200仪器上使用手性柱进行。配体4a - b和4e - h购自大赛璐手性技术(中国)有限公司。配体$4\mathrm{c}$和$4\mathbf{d}$按照文献合成。${}^{\left\lbrack {15},{16}\right\rbrack }$

General Experimental Procedure for the Synthesis of N-Tosylhydrazones

合成N-甲苯磺酰腙的一般实验步骤

The $N$ -tosylhydrazones 1a-k and 1l-s were prepared according to the literature procedures. ${}^{\left\lbrack {17},{18}\right\rbrack }$ The ketone (20 mmol) was added to the methanolic solution (30 mL) of $p$ -toluenesulfonhydrazide (20 mmol). The reaction mixture was refluxed for ${0.5} - 2\mathrm{\;h}$ . Then the mixture was allowed to cool to room temperature and the product precipitated. The crystalline product was collected by filtration and washed thoroughly with cold ether.

按照文献方法制备了$N$-甲苯磺酰腙1a-k和1l-s。${}^{\left\lbrack {17},{18}\right\rbrack }$ 将酮(20 mmol)加入到$p$-甲苯磺酰肼(20 mmol)的甲醇溶液(30 mL)中。反应混合物回流${0.5} - 2\mathrm{\;h}$。然后将混合物冷却至室温，产物沉淀。通过过滤收集结晶产物，并用冷乙醚彻底洗涤。

Typical Procedure for the Cu(I)/L*-Catalyzed Cou- pling Reaction

Cu(I)/L*催化的偶联反应的典型步骤

Condition A. In an oven dried ${10}\mathrm{\;{mL}}$ Schlenk tube equipped with a stirring bar, $\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}({3.7}\mathrm{{mg}}$ , 0.01 mmol, 5 mol%), ligand 4a (11.8 mg, 0.022 mmol, 11 mol%) were added into dioxane $\left( {{2.0}\mathrm{\;{mL}}}\right)$ under nitrogen atmosphere. The mixture was stirred for two hours at room temperature. Then ethynyltriiso-propylsilane 1 (0.2 mmol), $N$ -tosylhydrazones 2 (0.3 mmol) and ${\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}$ (0.6 mmol,195 mg) were added to the tube under nitrogen atmosphere. The reaction mixture was stirred for ${24}\mathrm{\;h}$ at ${70}^{ \circ }\mathrm{C}$ . Then the mixture was purified by silica gel column chromatography (eluted by petroleum ether) to afford the coupling product 3.

条件A。在一个装有搅拌棒的经烘箱干燥的${10}\mathrm{\;{mL}}$Schlenk管中，将$\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}({3.7}\mathrm{{mg}}$(0.01 mmol，5 mol%)、配体4a(11.8 mg，0.022 mmol，11 mol%)在氮气氛围下加入到二氧六环$\left( {{2.0}\mathrm{\;{mL}}}\right)$中。混合物在室温下搅拌两小时。然后在氮气氛围下将乙炔基三异丙基硅烷1(0.2 mmol)、$N$-甲苯磺酰腙2(0.3 mmol)和${\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}$(0.6 mmol，195 mg)加入到管中。反应混合物在${70}^{ \circ }\mathrm{C}$下搅拌${24}\mathrm{\;h}$。然后通过硅胶柱色谱法(用石油醚洗脱)纯化混合物，得到偶联产物3。

Condition B. In an oven dried ${10}\mathrm{\;{mL}}$ Schlenk tube equipped with a stirring bar, $\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}({3.7}\mathrm{{mg}}$ , 0.01 mmol, 5 mol%), ligand 4f (9.4 mg, 0.022 mmol, 11 mol%) were added into dioxane (2.0 mL) under nitrogen atmosphere. The mixture was stirred for $2\mathrm{\;h}$ at room temperature. Then ethynyltriisopropylsilane $1({0.2}$ mmol), $N$ -tosylhydrazone $2\left( {{0.3}\mathrm{{mmol}}}\right)$ and ${\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}({0.6}$ mmol, 195 mg) were added to the tube under nitrogen atmosphere. The reaction mixture was stirred for ${24}\mathrm{\;h}$ at ${70}^{ \circ }\mathrm{C}$ . Then the mixture was purified by silica gel column chromatography (eluted by petroleum ether) to afford the coupling product 3.

条件B。在一个装有搅拌棒的经烘箱干燥的${10}\mathrm{\;{mL}}$Schlenk管中，将$\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}({3.7}\mathrm{{mg}}$(0.01 mmol，5 mol%)、配体4f(9.4 mg，0.022 mmol，11 mol%)在氮气氛围下加入到二氧六环(2.0 mL)中。混合物在室温下搅拌$2\mathrm{\;h}$。然后在氮气氛围下将乙炔基三异丙基硅烷$1({0.2}$ mmol)、$N$-甲苯磺酰腙$2\left( {{0.3}\mathrm{{mmol}}}\right)$和${\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}({0.6}$ mmol，195 mg)加入到管中。反应混合物在${70}^{ \circ }\mathrm{C}$下搅拌${24}\mathrm{\;h}$。然后通过硅胶柱色谱法(用石油醚洗脱)纯化混合物，得到偶联产物3。

Triisopropyl(3-(3-methoxyphenyl)but-1-yn-1-yl)

三异丙基(3-(3-甲氧基苯基)丁-1-炔-1-基)

silane (3a). The title compound was obtained according to condition A: Colorless oil; yield 72% (45.5 mg). The ee was determined by HPLC analysis using Daicel Chi-ralpak OD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) = 11.8 min, t (minor) $= {11.0}\mathrm{\;{min}},{83}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {2.0}(c = {0.2}$ , ${\mathrm{{CHCl}}}_{3}).{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {7.22}$ (t, $J = {8.0} \; \mathrm{{Hz}},1\mathrm{H}),{7.03} - {7.01}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.96}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${6.79} - {6.75}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{3.81}\left( {\mathrm{q}, J = {6.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.80}\left( {\mathrm{\;s},3\mathrm{H}}\right)$ , ${1.50}\left( {\mathrm{\;d}, J = {6.8}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.07}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {159.7},{144.9},{129.3},{119.3}$ , 112.3, 112.2, 111.1, 82.4, 55.1, 33.0, 25.1, 18.6, 11.3. IR: $v = {2945},{2868},{2162},{1606},{1473},{1256},{1126},{1018}$ , 864,749,663 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{20}{\mathrm{H}}_{33}\mathrm{{OSi}}$ : 317.2295; found: 317.2294.

硅烷(3a)。按照条件A得到标题化合物:无色油状物；产率72%(45.5毫克)。通过使用大赛璐Chiralpak OD-H柱的HPLC分析测定对映体过量，条件:$n$ -己烷$/i$ -丙醇 = 100:0，0.5毫升/分钟，220纳米；t(主峰)= 11.8分钟，t(次峰)$= {11.0}\mathrm{\;{min}},{83}\%$ 对映体过量；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {2.0}(c = {0.2}$ ，${\mathrm{{CHCl}}}_{3}).{}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ )$\delta = {7.22}$ (t，$J = {8.0} \; \mathrm{{Hz}},1\mathrm{H}),{7.03} - {7.01}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.96}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ ，${6.79} - {6.75}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{3.81}\left( {\mathrm{q}, J = {6.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.80}\left( {\mathrm{\;s},3\mathrm{H}}\right)$ ，${1.50}\left( {\mathrm{\;d}, J = {6.8}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.07}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {159.7},{144.9},{129.3},{119.3}$ ，112.3，112.2，111.1，82.4，55.1，33.0，25.1，18.6，11.3。红外光谱:$v = {2945},{2868},{2162},{1606},{1473},{1256},{1126},{1018}$ ，864,749,663 ${\mathrm{{cm}}}^{-1}$ ；高分辨质谱(电喷雾电离):$m/z$ 计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{20}{\mathrm{H}}_{33}\mathrm{{OSi}}$ :317.2295；实测值:317.2294。

Triisopropyl(3-phenylbut-1-yn-1-yl)silane (3b). ${}^{\left\lbrack {19}\right\rbrack }$ The title compound was obtained according to condition A: Colorless oil; yield 70% (40.0 mg). Chiral GC analysis of the product: Chirasil Dex CB column; method: ${100}{}^{ \circ }\mathrm{C} \rightarrow {130}{}^{ \circ }\mathrm{C}$ @ ${10}{}^{ \circ }\mathrm{C}/\mathrm{{min}}$ , hold ${10}\mathrm{\;{min}}$ , then $\rightarrow {170}{}^{ \circ }\mathrm{C}$ @ $9{}^{ \circ }\mathrm{C}/\mathrm{{min}}$ , hold 5 min; flow rate 0.5 mL/min; retention times: 35.7 min (major), 35.8 min (minor), ${75}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {3.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, CDCl1) 5 = 7.42-7.39 (m, 2H), 7.34-7.29 (m, 2H), 7.24-7.18 (m, 1H), 3.81 (q, J = 7.2 $\mathrm{{Hz}},1\mathrm{H}),{1.50}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.06}\left( {\mathrm{\;m},{21}\mathrm{H}}\right)$ ; ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {143.3},{128.4},{126.9}$ , 126.5, 111.2, 82.3, 32.9, 25.1, 18.6, 11.3.

三异丙基(3-苯基丁-1-炔-1-基)硅烷(3b)。${}^{\left\lbrack {19}\right\rbrack }$ 标题化合物根据条件A制备:无色油状物；产率70%(40.0毫克)。产物的手性气相色谱分析:Chirasil Dex CB柱；方法:${100}{}^{ \circ }\mathrm{C} \rightarrow {130}{}^{ \circ }\mathrm{C}$ @ ${10}{}^{ \circ }\mathrm{C}/\mathrm{{min}}$ ，保持 ${10}\mathrm{\;{min}}$ ，然后 $\rightarrow {170}{}^{ \circ }\mathrm{C}$ @ $9{}^{ \circ }\mathrm{C}/\mathrm{{min}}$ ，保持5分钟；流速0.5毫升/分钟；保留时间:35.7分钟(主峰)，35.8分钟(次峰)，${75}\%$ ee；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {3.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR(400兆赫兹，CDCl1)δ = 7.42 - 7.39(m，2H)，7.34 - 7.29(m，2H)，7.24 - 7.18(m，1H)，3.81(q，J = 7.2 $\mathrm{{Hz}},1\mathrm{H}),{1.50}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.06}\left( {\mathrm{\;m},{21}\mathrm{H}}\right)$ ；${}^{13}\mathrm{C}$ NMR(100兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta = {143.3},{128.4},{126.9}$ ，126.5，111.2，82.3，32.9，25.1，18.6，11.3。

Triisopropyl(3-(4-methoxyphenyl)but-1-yn-1-yl)

三异丙基(3-(4-甲氧基苯基)丁-1-炔-1-基)

silane (3c). ${}^{\left\lbrack {19}\right\rbrack }$ The title compound was prepared according to condition A: Colorless oil; yield 80% (50.5 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane/i-PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) $= {23.9}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {23.0}\mathrm{\;{min}},{70}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {8.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = \; {7.34} - {7.30}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{6.89} - {6.83}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{3.79}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{3.76} \; \left( {\mathrm{q}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.48}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.06} \; \left( {\mathrm{m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {158.2},{135.5}$ , 127.8, 113.7, 111.6, 82.0, 55.2, 32.1, 25.2, 18.6, 11.3.

硅烷(3c)。${}^{\left\lbrack {19}\right\rbrack }$ 标题化合物按照条件A制备:无色油状物；产率80%(50.5毫克)。对映体过量值通过使用大赛璐手性派克2xOD-H柱的HPLC分析测定，条件:$n$ -己烷/异丙醇 = 100:0，0.5毫升/分钟，220纳米；t(主要)$= {23.9}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {23.0}\mathrm{\;{min}},{70}\%$ 对映体过量值；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {8.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ 核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = \; {7.34} - {7.30}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{6.89} - {6.83}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{3.79}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{3.76} \; \left( {\mathrm{q}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.48}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.06} \; \left( {\mathrm{m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {158.2},{135.5}$ ，127.8，113.7，111.6，82.0，55.2，32.1，25.2，18.6，11.3。

(3-([1,1’-Biphenyl]-4-yl)but-1-yn-1-yl)triisoprop ylsilane (3d). The title compound was obtained according to condition A: Colorless oil; yield 40% (28.9 mg). The ee was determined by HPLC analysis using

(3-([1,1’-联苯]-4-基)丁-1-炔-1-基)三异丙基硅烷(3d)。标题化合物按照条件A获得:无色油状物；产率40%(28.9毫克)。对映体过量值通过使用

Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, ${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ; t (major) $= {45.5}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {57.0}\mathrm{\;{min}},{79}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {1.5}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = \; {7.63} - {7.55}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.52} - {7.42}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.38} - {7.32}(\mathrm{\;m}$ , 1H), ${3.88}\left( {\mathrm{q}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.56}\left( {\mathrm{\;d}, J = {7.2}\mathrm{{Hz}},3\mathrm{H}}\right)$ , 1.13-1.10 $\left( {\mathrm{m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 142.4, 140.9, 139.4, 128.7, 127.3, 127.2, 127.1, 127.0, 111.1, 82.4, 32.6, 25.1, 18.7, 11.3. IR: v= 2942, 2868, 2159, 1460, 1262, 1114, 996, 817, 768 cm ${}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{25}{\mathrm{H}}_{34}\mathrm{{Si}} : {362.2424}$ ; found: 362.2425.

大赛璐手性派克2xOD-H柱，条件:$n$ -己烷$/i$ -异丙醇 = 100:0，${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$；t(主峰)$= {45.5}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {57.0}\mathrm{\;{min}},{79}\%$ ee；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {1.5}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = \; {7.63} - {7.55}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.52} - {7.42}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.38} - {7.32}(\mathrm{\;m}$，1H)，${3.88}\left( {\mathrm{q}, J = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.56}\left( {\mathrm{\;d}, J = {7.2}\mathrm{{Hz}},3\mathrm{H}}\right)$，1.13 - 1.10$\left( {\mathrm{m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 142.4，140.9，139.4，128.7，127.3，127.2，127.1，127.0，111.1，82.4，32.6，25.1，18.7，11.3。红外光谱:v = 2942，2868，2159，1460，1262，1114，996，817，768 cm${}^{-1}$；高分辨质谱(电子电离):$m/z$计算值为${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{25}{\mathrm{H}}_{34}\mathrm{{Si}} : {362.2424}$；实测值:362.2425。

(3-(4-Bromophenyl)but-1-yn-1-yl)triisopropylsila

(3-(4-溴苯基)丁-1-炔-1-基)三异丙基硅烷

ne (3e). The title compound was obtained according to condition A: Colorless oil; yield ${74}\% \left( {{54.0}\mathrm{{mg}}}\right) .{\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {2.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 7.46-7.42 (m, 2H), 7.30-7.27 (m, 2H), 3.77 (q, J = 7.2 $\mathrm{{Hz}},1\mathrm{H}),{1.47}\left( {\mathrm{\;d}, J = {7.2}\mathrm{{Hz}},3\mathrm{H}}\right) ,{1.09} - {1.06}\left( {\mathrm{\;m},{21}\mathrm{H}}\right)$ ; ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {142.3},{131.5},{128.7}$ , 120.3, 110.5, 82.8, 32.5, 24.9, 18.6, 11.3; IR: v= 2939, 2864, 2172, 1488, 1461, 1266, 1012, 824, 678 cm ${}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{19}{\mathrm{H}}_{29}\mathrm{{BrSi}} : {364.1216}$ ; found: 364.1213.

(3e)。根据条件A得到标题化合物:无色油状物；产率${74}\% \left( {{54.0}\mathrm{{mg}}}\right) .{\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {2.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ 核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 7.46 - 7.42(m，2H)，7.30 - 7.27(m，2H)，3.77(q，J = 7.2 $\mathrm{{Hz}},1\mathrm{H}),{1.47}\left( {\mathrm{\;d}, J = {7.2}\mathrm{{Hz}},3\mathrm{H}}\right) ,{1.09} - {1.06}\left( {\mathrm{\;m},{21}\mathrm{H}}\right)$；${}^{13}\mathrm{C}$ 核磁共振(100 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta = {142.3},{131.5},{128.7}$，120.3，110.5，82.8，32.5，24.9，18.6，11.3；红外光谱:v = 2939，2864，2172，1488，1461，1266，1012，824，678 cm${}^{-1}$；高分辨质谱(EI):$m/z$ 计算值为${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{19}{\mathrm{H}}_{29}\mathrm{{BrSi}} : {364.1216}$；实测值:364.1213。

1-Bromo-4-(but-3-yn-2-yl)benzene (3e’). The title compound was obtained by removal of the TIPS group of 3e with tetrabutylammonium fluoride in THF (1.0 M): Colorless oil; yield 75% (31.3 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH $= {100} : 0$ , ${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}};\mathrm{t}\left( \mathrm{{major}}\right) = {28.5}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = \; {26.3}\mathrm{\;{min}},{63}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = - {3.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) .{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ = 7.47-7.43 (m, 2H), 7.28-7.27 (m, 2H), 3.88 (dq, J = 2.4, 7.2 Hz, 1H), 2.27 $\left( {\mathrm{d}, J = {2.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.48}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}} \; \left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {141.6},{131.6},{128.6},{120.5},{86.4}$ , 70.5,31.1,24.1; IR: $v = {2929},{2852},{2360},{1643},{1362}$ , 1062,848,789 ${\mathrm{{cm}}}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M}\right\rbrack }^{ + } \; {\mathrm{C}}_{10}{\mathrm{H}}_{9}\mathrm{{Br}}$ 207.9882; found: 207.9878.

1-溴-4-(3-丁炔-2-基)苯(3e’)。通过在四氢呋喃(1.0M)中用四丁基氟化铵除去3e的TIPS基团得到标题化合物:无色油状物；产率75%(31.3mg)。通过使用Daicel Chiralpak 2xOD-H柱的HPLC分析测定ee，条件:$n$ -己烷$/i$ -丙醇$= {100} : 0$ ，${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}};\mathrm{t}\left( \mathrm{{major}}\right) = {28.5}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = \; {26.3}\mathrm{\;{min}},{63}\%$ ee；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = - {3.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) .{}^{1}\mathrm{H}$ NMR(400MHz，CDCl3)δ = 7.47-7.43(m，2H)，7.28-7.27(m，2H)，3.88(dq，J = 2.4，7.2Hz，1H)，2.27$\left( {\mathrm{d}, J = {2.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{1.48}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}} \; \left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {141.6},{131.6},{128.6},{120.5},{86.4}$ ，70.5，31.1，24.1；IR:$v = {2929},{2852},{2360},{1643},{1362}$ ，1062，848，789${\mathrm{{cm}}}^{-1}$ ；HRMS(EI):$m/z$ 计算值为${\left\lbrack \mathrm{M}\right\rbrack }^{ + } \; {\mathrm{C}}_{10}{\mathrm{H}}_{9}\mathrm{{Br}}$ 207.9882；实测值:207.9878。

Triisopropyl(3-(3,4,5-trimethoxyphenyl)but-1-yn- 1-yl)silane (3f). The title compound was obtained according to condition A: Colorless oil; yield 45% (33.8 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane/i-PrOH = 98:2, 0.5 mL/min, 220 nm; t (major) $= {19.0}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {20.4}\mathrm{\;{min}},{74}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {5.0} \; \left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {6.66} \; \left( {\mathrm{s},2\mathrm{H}}\right) ,{3.85}\left( {\mathrm{\;s},6\mathrm{H}}\right) ,{3.83}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{3.76}(\mathrm{q}, J = {7.2}\mathrm{\;{Hz}}$ , $1\mathrm{H}),{1.49}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.06}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ = 153.0, 138.9, 136.3, 111.0, 103.7, 82.5, 60.7, 55.9, 33.2, 25.3, 18.6, 11.2; IR: v= 2933, 2864, 2169, 1590, 1463, 1235, 1130, 1006, 876, ${718},{656}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{22}{\mathrm{H}}_{37}{\mathrm{O}}_{3}\mathrm{{Si}} : {377.2506}$ ; found: 377.2515.

三异丙基(3-(3,4,5-三甲氧基苯基)丁-1-炔-1-基)硅烷(3f)。按照条件A得到标题化合物:无色油状物；产率45%(33.8毫克)。通过使用大赛璐手性派克2xOD-H柱的HPLC分析测定对映体过量，条件:$n$ -己烷/异丙醇 = 98:2，0.5毫升/分钟，220纳米；t(主峰)$= {19.0}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {20.4}\mathrm{\;{min}},{74}\%$ 对映体过量；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {5.0} \; \left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR(400兆赫，${\mathrm{{CDCl}}}_{3}$ )$\delta = {6.66} \; \left( {\mathrm{s},2\mathrm{H}}\right) ,{3.85}\left( {\mathrm{\;s},6\mathrm{H}}\right) ,{3.83}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{3.76}(\mathrm{q}, J = {7.2}\mathrm{\;{Hz}}$ ，$1\mathrm{H}),{1.49}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.10} - {1.06}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR(100兆赫，CDCl3)δ = 153.0，138.9，136.3，111.0，103.7，82.5，60.7，55.9，33.2，25.3，18.6，11.2；IR:v = 2933，2864，2169，1590，1463，1235，1130，1006，876，${718},{656}{\mathrm{\;{cm}}}^{-1}$ ；高分辨质谱(电喷雾电离):$m/z$ 计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{22}{\mathrm{H}}_{37}{\mathrm{O}}_{3}\mathrm{{Si}} : {377.2506}$ ；实测值:377.2515。

Triisopropyl(3-(naphthalen-1-yl)but-1-yn-1-yl)

三异丙基(3-(萘-1-基)丁-1-炔-1-基)

silane (3g). ${}^{\left\lbrack {19}\right\rbrack }$ The title compound was obtained according to condition A: Colorless oil; yield 52% (34.9 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xAD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, ${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ; t (major) $= {16.0}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.9}\mathrm{\;{min}},{52}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {1.9}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) ;{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta =$ 8.14-8.10 (m, 1H), 7.90-7.82 (m, 2H), 7.78-7.74 (m, 1H), 7.55-7.45 (m, 3H), 4.59 (q, J = 7.2 Hz, 1H), 1.66 $\left( {\mathrm{d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.13} - {1.10}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDC1, 5 = 138.9, 133.9, 130.5, 128.9, 127.3, 125.9, 125.6, 125.4, 124.3, 123.2, 111.5, 82.7, 29.7, 23.9, 18.7, 11.3.

硅烷(3g)。${}^{\left\lbrack {19}\right\rbrack }$ 标题化合物根据条件A制得:无色油状物；产率52%(34.9毫克)。对映体过量值通过使用大赛璐手性派克2xAD-H柱的HPLC分析测定，条件:$n$ -己烷$/i$ -异丙醇 = 100:0，${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ；t(主要)$= {16.0}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.9}\mathrm{\;{min}},{52}\%$ 对映体过量值；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {1.9}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) ;{}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta =$ 8.14 - 8.10(多重峰，1H)，7.90 - 7.82(多重峰，2H)，7.78 - 7.74(多重峰，1H)，7.55 - 7.45(多重峰，3H)，4.59(四重峰，J = 7.2赫兹，1H)，1.66 $\left( {\mathrm{d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ,{1.13} - {1.10}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100兆赫，CDCl₃，δ = 138.9，133.9，130.5，128.9，127.3，125.9，125.6，125.4，124.3，123.2，111.5，82.7，29.7，23.9，18.7，11.3。

Triisopropyl(3-(naphthalen-2-yl)but-1-yn-1-yl)

三异丙基(3-(萘-2-基)丁-1-炔-1-基)

silane (3h). The title compound was obtained according to condition A: Colorless oil; yield 60% (40.3 mg). The ee was determined by HPLC analysis using Daicel Chi-ralpak OD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) = 12.7 min, t (minor) = 14.4 min, 79% ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{{20}^{ \circ }} = + {1.8}(c = {0.2}$ , $\left. {\mathrm{{CHCl}}}_{3}\right) \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {7.96}\left( {\mathrm{\;S},1\mathrm{H}}\right)$ , ${7.88} - {7.83}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.57}\left( {\mathrm{{dd}}, J = {1.6},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${7.54} - {7.46}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{4.03}\left( {\mathrm{q}, J = {7.2}\mathrm{{Hz}},1\mathrm{H}}\right) ,{1.64}(\mathrm{\;d}, J = \; {7.2}\mathrm{\;{Hz}},3\mathrm{H}),{1.20} - {1.15}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3})\delta = {140.7},{133.5},{132.3},{128.1},{127.7},{127.6}$ , 126.0, 125.6, 125.5, 125.2, 111.2, 82.6, 33.1, 24.9, 18.6, 11.3; IR: $v = {2976},{2895},{2169},{1402},{1265},{1061},{891}$ , 836,740,653 ${\mathrm{{cm}}}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M}\right\rbrack }^{ + } \; {\mathrm{C}}_{23}{\mathrm{H}}_{32}\mathrm{{Si}}$ : 336.2267; found: 336.2264.

硅烷(3h)。标题化合物按照条件A制备得到:无色油状物；产率60%(40.3毫克)。对映体过量值通过使用大赛璐手性pak OD-H柱的HPLC分析测定，条件:$n$ -己烷$/i$ -丙醇 = 100:0，0.5毫升/分钟，220纳米；t(主峰)= 12.7分钟，t(次峰)= 14.4分钟，对映体过量值79%；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{{20}^{ \circ }} = + {1.8}(c = {0.2}$ ，$\left. {\mathrm{{CHCl}}}_{3}\right) \cdot {}^{1}\mathrm{H}$ 核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta = {7.96}\left( {\mathrm{\;S},1\mathrm{H}}\right)$ ，${7.88} - {7.83}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.57}\left( {\mathrm{{dd}}, J = {1.6},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ ，${7.54} - {7.46}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{4.03}\left( {\mathrm{q}, J = {7.2}\mathrm{{Hz}},1\mathrm{H}}\right) ,{1.64}(\mathrm{\;d}, J = \; {7.2}\mathrm{\;{Hz}},3\mathrm{H}),{1.20} - {1.15}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3})\delta = {140.7},{133.5},{132.3},{128.1},{127.7},{127.6}$ ，126.0，125.6，125.5，125.2，111.2，82.6，33.1，24.9，18.6，11.3；红外光谱:$v = {2976},{2895},{2169},{1402},{1265},{1061},{891}$ ，836,740,653 ${\mathrm{{cm}}}^{-1}$ ；高分辨质谱(电子轰击电离):$m/z$ 计算值为${\left\lbrack \mathrm{M}\right\rbrack }^{ + } \; {\mathrm{C}}_{23}{\mathrm{H}}_{32}\mathrm{{Si}}$ :336.2267；实测值:336.2264。

Triisopropyl(3-(6-methoxynaphthalen-2-yl)but

三异丙基(3-(6-甲氧基萘-2-基)丁

-1-yn-1-yl)silane (3i). The title compound was obtained according to condition A: Colorless oil; yield 50% (36.7 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH $= {100} : 0,{0.5}\mathrm{\;{mL}}/\mathrm{{min}}$ , 220 nm; t (major) $= {67.9}\mathrm{\;{min}},\mathrm{t}$ (minor) $= {58.6}\mathrm{\;{min}}$ , 55% ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {1.8}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3})\delta = {7.84}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.72} - {7.69}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ , 7.51-7.45 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{7.17} - {7.12}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{3.95}\left( {\mathrm{q}, J = {7.2}}\right) \; \mathrm{{Hz}},1\mathrm{H}),{3.92}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.58}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right)$ , 1.15-1.10 (m, 21H) ppm. ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {157.4},{138.4},{133.4},{129.2},{128.9},{126.9},{126.1}$ , 125.0, 118.8, 111.4, 105.6, 82.4, 55.3, 32.9, 24.9, 18.7,11.3 ppm. IR: $v = {2982},{2905},{2175},{1618},{1405}$ , 1238,1052,907,873,727 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{24}{\mathrm{H}}_{35}\mathrm{{OSi}} : {367.2451}$ ; found: 367.2450.

-1-炔基)硅烷(3i)。标题化合物按照条件A制得:无色油状物；产率50%(36.7毫克)。对映体过量值通过使用大赛璐手性派克2xOD-H柱的HPLC分析测定，条件:$n$ -己烷$/i$ -丙醇$= {100} : 0,{0.5}\mathrm{\;{mL}}/\mathrm{{min}}$ ，220纳米；t(主峰)$= {67.9}\mathrm{\;{min}},\mathrm{t}$ (次峰)$= {58.6}\mathrm{\;{min}}$ ，对映体过量值55%；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {1.8}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3})\delta = {7.84}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{7.72} - {7.69}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ ，7.51 - 7.45$\left( {\mathrm{m},1\mathrm{H}}\right) ,{7.17} - {7.12}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{3.95}\left( {\mathrm{q}, J = {7.2}}\right) \; \mathrm{{Hz}},1\mathrm{H}),{3.92}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.58}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right)$ ，1.15 - 1.10(多重峰，21H)百万分之一。${}^{13}\mathrm{C}$ 核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$ )$\delta = {157.4},{138.4},{133.4},{129.2},{128.9},{126.9},{126.1}$ ，125.0，118.8，111.4，105.6，82.4，55.3，32.9，24.9，18.7，11.3百万分之一。红外光谱:$v = {2982},{2905},{2175},{1618},{1405}$ ，1238，1052，907，873，727${\mathrm{{cm}}}^{-1}$ ；高分辨质谱(电喷雾电离):$m/z$ 计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{24}{\mathrm{H}}_{35}\mathrm{{OSi}} : {367.2451}$ ；实测值:367.2450。

Triisopropyl(3-(4-methoxyphenyl)pent-1-yn-1-yl)

三异丙基(3-(4-甲氧基苯基)戊-1-炔-1-基)

silane (3j). The title compound was obtained according to condition A: Colorless oil; yield 76% (50.2 mg). The ee was determined by HPLC analysis using Daicel Chi-ralpak 2xOD-H column, conditions: n-hexane/i-PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) = 21.0 min, t (minor) $= {19.7}\mathrm{\;{min}},{46}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{{20}^{ \circ }} = + {3.0}\left( {c = {0.2}}\right.$ , ${\mathrm{{CHCl}}}_{3}).{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {7.33} - {7.29}(\mathrm{\;m}$ , 2H), 6.89-6.85 (m, 2H), 3.81 (s, 3H), 3.65-3.60 (m, 1H), 1.90-1.66 (m, 2H), 1.15-1.10 (m, 21H), 1.02 (t, J = 7.2 Hz, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta = {158.2},{134.1}$ , 128.4, 113.6, 110.2, 82.9, 55.2, 39.5, 32.1, 18.7, 11.6, 11.3 ppm. IR: $v = {2967},{2864},{2165},{1519},{1250},{1046}$ , ${882},{805},{663}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{21}{\mathrm{H}}_{35}\mathrm{{OSi}}$ : 331.2451; found: 331.2453.

硅烷(3j)。按照条件A得到标题化合物:无色油状物；产率76%(50.2毫克)。对映体过量值通过使用大赛璐手性pak 2xOD-H柱的HPLC分析测定，条件:正己烷/异丙醇 = 100:0，0.5毫升/分钟，220纳米；t(主峰)= 21.0分钟，t(次峰)$= {19.7}\mathrm{\;{min}},{46}\%$ 对映体过量值；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{{20}^{ \circ }} = + {3.0}\left( {c = {0.2}}\right.$ ，${\mathrm{{CHCl}}}_{3}).{}^{1}\mathrm{H}$ NMR(4百公里兆赫，${\mathrm{{CDCl}}}_{3}$ )$\delta = {7.33} - {7.29}(\mathrm{\;m}$ ，2H)，6.89 - 6.85(多重峰，2H)，3.81(单峰，3H)，3.65 - 3.60(多重峰，1H)，1.90 - 1.66(多重峰，2H)，1.15 - 1.10(多重峰，21H)，1.02(三重峰，J = 7.2赫兹，3H)；${}^{13}\mathrm{C}$ NMR(100兆赫，CDCl3)$\delta = {158.2},{134.1}$ ，128.4，113.6，110.2，82.9，55.2，39.5，32.1，18.7，11.6，11.3 ppm。红外光谱:$v = {2967},{2864},{2165},{1519},{1250},{1046}$ ，${882},{805},{663}{\mathrm{\;{cm}}}^{-1}$ ；高分辨质谱(电喷雾电离):$m/z$ 计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{21}{\mathrm{H}}_{35}\mathrm{{OSi}}$ :331.2451；实测值:331.2453。

(3-(Benzo[d][1,3]dioxol-5-yl)hex-1-yn-1-yl)triisopr opylsilane (3k). The title compound was obtained according to condition A: Colorless oil; yield 60% (43.0 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane/i-PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) $= {22.4}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {23.2}\mathrm{\;{min}},{42}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {7.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 6.92-6.89 (m, 1H), 6.85-6.80 (m, 1H), 6.77-6.73 (m, 1H), 5.95-5.93 (m, 2H), 3.66-3.61 (m, 1H), 1.72-1.63 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{1.54} - {1.40}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.11} - {1.08}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ,{0.92}(\mathrm{t}$ , $J = {7.2}\mathrm{\;{Hz}},3\mathrm{H});{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {147.5}$ , 146.0, 136.3, 120.4, 110.2, 108.0, 107.9, 100.9, 83.0, 41.4, 38.3, 20.4, 18.6, 13.7, 11.3; IR: $v = {2945},{2862}$ , 2163,1492,1250,1052,885,675 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}{\mathrm{O}}_{2}\mathrm{{Si}} : {359.2400}$ ; found: 359.2401.

(3-(苯并[d][1,3]二氧杂环戊烯-5-基)己-1-炔-1-基)三异丙基硅烷(3k)。根据条件A得到标题化合物:无色油状物；产率60%(43.0毫克)。通过使用大赛璐手性pak 2xOD-H柱的HPLC分析测定ee值，条件:$n$ -己烷/异丙醇 = 100:0，0.5毫升/分钟，220纳米；t(主要)$= {22.4}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {23.2}\mathrm{\;{min}},{42}\%$ ee；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {7.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 6.92 - 6.89(m，1H)，6.85 - 6.80(m，1H)，6.77 - 6.73(m，1H)，5.95 - 5.93(m，2H)，3.66 - 3.61(m，1H)，1.72 - 1.63 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{1.54} - {1.40}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.11} - {1.08}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ,{0.92}(\mathrm{t}$ ，$J = {7.2}\mathrm{\;{Hz}},3\mathrm{H});{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {147.5}$ ，146.0，136.3，120.4，110.2，108.0，107.9，100.9，83.0，41.4，38.3，20.4，18.6，13.7，11.3；IR:$v = {2945},{2862}$ ，2163,1492,1250,1052,885,675 ${\mathrm{{cm}}}^{-1}$ ；HRMS(ESI):$m/z$ 计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}{\mathrm{O}}_{2}\mathrm{{Si}} : {359.2400}$ ；实测值:359.2401。

Triisopropyl((1,2,3,4-tetrahydronaphthalen-1-yl)

三异丙基((1,2,3,4-四氢萘-1-基)

ethynyl)silane (3l). The title compound was obtained according to condition B: Colorless oil; yield 80% (49.9 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, ${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ; t (major) $= {17.6}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.6}\mathrm{\;{min}},{82}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {4.9}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 7.55-7.50 (m, 1H), 7.19-7.11 (m, 2H), 7.08-7.05 (m, 1H), 3.84 (dd, J = 5.2, 8.4 Hz, 1H), 2.90-2.70 (m, 2H), 2.20-2.10 (m, 1H), 2.05-1.95 (m, 1H), 1.94-1.84 (m, 1H), 1.81-1.70 (m, 1H), 1.08-1.04 (m, 21H); ${}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {136.4},{136.0},{129.0},{128.9}$ , 126.3, 125.8, 111.6, 81.0, 32.6, 30.6, 29.1, 21.4, 18.6, 11.3; IR: $v = {2939},{2864},{2169},{1457},{1074},{1018},{876}$ , ${746},{669}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{21}{\mathrm{H}}_{32}\mathrm{{Si}}$ : 312.2267; found: 312.2267.

乙炔基硅烷(3l)。标题化合物按照条件B制备:无色油状物；产率80%(49.9毫克)。对映体过量值通过使用大赛璐手性派克2xOD - H柱的HPLC分析测定，条件:$n$ -己烷$/i$ -异丙醇 = 100:0，${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ；t(主峰)$= {17.6}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.6}\mathrm{\;{min}},{82}\%$ 对映体过量值；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {4.9}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ 核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta =$ 7.55 - 7.50(m，1H)，7.19 - 7.11(m，2H)，7.08 - 7.05(m，1H)，3.84(dd，J = 5.2，8.4赫兹，1H)，2.90 - 2.70(m，2H)，2.20 - 2.10(m，1H)，2.05 - 1.95(m，1H)，1.94 - 1.84(m，1H)，1.81 - 1.70(m，1H)，1.08 - 1.04(m，21H)；${}^{13}\mathrm{C}$ 核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {136.4},{136.0},{129.0},{128.9}$ ，126.3，125.8，111.6，81.0，32.6，30.6，29.1，21.4，18.6，11.3；红外光谱:$v = {2939},{2864},{2169},{1457},{1074},{1018},{876}$ ，${746},{669}{\mathrm{\;{cm}}}^{-1}$ ；高分辨质谱(电子轰击电离):$m/z$ 计算值为${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{21}{\mathrm{H}}_{32}\mathrm{{Si}}$ :312.2267；实测值:312.2267。

((7-Bromo-1,2,3,4-tetrahydronaphthalen-1-yl)eth ynyl)triisopropylsilane (3m). The title compound was obtained according to condition B: Colorless oil; yield 82% (64.1 mg). The ee was obtained by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, ${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ; t (major) $= {20.1}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {18.3}\mathrm{\;{min}},{72}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {2.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = \; {7.69}\left( {\mathrm{\;d}, J = {1.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.26} - {7.22}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.92}(\mathrm{\;d}, J = \; {8.4}\mathrm{\;{Hz}},1\mathrm{H}),{3.77}\left( {\mathrm{{dd}}, J = {5.2},{8.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.80} - {2.65} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{2.18} - {2.10}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.03} - {1.94}\left( {\mathrm{\;m},1\mathrm{H}}\right)$ , 1.89-1.80 (m, 1H), 1.78-1.66 (m, 1H), 1.08-1.04 (m, 21H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {138.6},{134.9}$ , 131.8, 130.5, 129.4, 119.3, 110.6, 82.0, 32.6, 30.1, 28.5, 21.2,18.6,11.3; IR: $v = {2945},{2856},{2163},{1594},{1476}$ , 1000,889,805,678 ${\mathrm{{cm}}}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{21}{\mathrm{H}}_{31}\mathrm{{BrSi}} : {390.1372}$ ; found: 390.1370.

((7-溴-1,2,3,4-四氢萘-1-基)乙炔基)三异丙基硅烷(3m)。按照条件B得到标题化合物:无色油状物；产率82%(64.1mg)。通过使用大赛璐手性派克2xOD-H柱的HPLC分析获得ee值，条件:$n$ -己烷$/i$ -异丙醇 = 100:0，${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ；t(主要)$= {20.1}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {18.3}\mathrm{\;{min}},{72}\%$ ee；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = \; + {2.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = \; {7.69}\left( {\mathrm{\;d}, J = {1.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.26} - {7.22}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.92}(\mathrm{\;d}, J = \; {8.4}\mathrm{\;{Hz}},1\mathrm{H}),{3.77}\left( {\mathrm{{dd}}, J = {5.2},{8.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.80} - {2.65} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{2.18} - {2.10}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.03} - {1.94}\left( {\mathrm{\;m},1\mathrm{H}}\right)$ ，1.89 - 1.80(m，1H)，1.78 - 1.66(m，1H)，1.08 - 1.04(m，21H)；${}^{13}\mathrm{C}$ NMR(100MHz，${\mathrm{{CDCl}}}_{3}$ )$\delta = {138.6},{134.9}$ ，131.8，130.5，129.4，119.3，110.6，82.0，32.6，30.1，28.5，21.2，18.6,11.3；IR:$v = {2945},{2856},{2163},{1594},{1476}$ ，1000,889,805,678${\mathrm{{cm}}}^{-1}$ ；HRMS(EI):$m/z$ 计算值为${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{21}{\mathrm{H}}_{31}\mathrm{{BrSi}} : {390.1372}$ ；实测值:390.1370。

Triisopropyl((7-methyl-1,2,3,4-tetrahydronaphth-alen-1-yl)ethynyl)silane (3n). The title compound was obtained according to condition B: Colorless oil; yield 65% (42.4 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: n-hexane/i-PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) $= {17.6}\mathrm{\;{min}}, t$ (minor) $= {15.8}\mathrm{\;{min}},{67}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {6.7}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ $= {7.40}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{6.96}\left( {\mathrm{\;d}, J = {0.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.81}(\mathrm{{dd}}, J =$ 5.2, ${8.8}\mathrm{\;{Hz}},1\mathrm{H}),{2.84} - {2.68}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{2.32}\left( {\mathrm{\;s},3\mathrm{H}}\right)$ , 2.20-2.12 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{2.04} - {1.95}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.93} - {1.83}(\mathrm{\;m}$ , 1H), 1.78-1.68 (m, 1H), 1.12-1.05 (m, 21H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl1) 5 = 136.1, 135.2, 132.9, 129.6, 128.8, 127.2, 111.8, 80.9, 32.7, 30.6, 28.7, 21.7, 20.9, 18.6,11.3; IR: $v = {2942},{2861},{2169},{1662},{1467},{1262}$ , 1006,888,793 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}\mathrm{{Si}} : {327.2502}$ ; found: 327.2502.

三异丙基((7-甲基-1,2,3,4-四氢萘-1-基)乙炔基)硅烷(3n)。按照条件B得到标题化合物:无色油状物；产率65%(42.4毫克)。通过使用大赛璐手性派克2xOD-H柱的HPLC分析测定对映体过量，条件:正己烷/异丙醇=100:0，0.5毫升/分钟，220纳米；t(主峰)$= {17.6}\mathrm{\;{min}}, t$(次峰)$= {15.8}\mathrm{\;{min}},{67}\%$对映体过量；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {6.7}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)δ$= {7.40}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{6.96}\left( {\mathrm{\;d}, J = {0.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.81}(\mathrm{{dd}}, J =$5.2，${8.8}\mathrm{\;{Hz}},1\mathrm{H}),{2.84} - {2.68}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{2.32}\left( {\mathrm{\;s},3\mathrm{H}}\right)$，2.20 - 2.12$\left( {\mathrm{m},1\mathrm{H}}\right) ,{2.04} - {1.95}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.93} - {1.83}(\mathrm{\;m}$，1H)，1.78 - 1.68(m，1H)，1.12 - 1.05(m，21H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl1)5 = 136.1，135.2，132.9，129.6，128.8，127.2，111.8，80.9，32.7，30.6，28.7，21.7，20.9，18.6，11.3；红外光谱:$v = {2942},{2861},{2169},{1662},{1467},{1262}$，1006,888,793${\mathrm{{cm}}}^{-1}$；高分辨质谱(电喷雾电离):$m/z$计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}\mathrm{{Si}} : {327.2502}$；实测值:327.2502。

((6-Fluoro-1,2,3,4-tetrahydronaphthalen-1-yl)ethy nyl)triisopropylsilane (30). The title compound was prepared according to condition B: Colorless oil; yield 45% (29.7 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: n-hexane/i-PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) $= {16.9}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.1}\mathrm{\;{min}},{66}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {3.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta \; = {7.48} - {7.43}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.88} - {6.81}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.77} - {6.73}(\mathrm{\;m}$ , 1H), 3.80-3.75 (m, 1H), 2.86-2.68 (m, 2H), 2.16-2.09 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{2.03} - {1.92}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.91} - {1.83}\left( {\mathrm{\;m},1\mathrm{H}}\right)$ , 1.78-1.68 (m, 1H), 1.07-1.03 (m, 21H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDC1s) δ = 162.5, 160.1, 138.1, 138.0, 132.05, 132.02, 130.5, 130.4, 115.1, 114.9, 113.0, 112.7, 111.4, 81.3, 32.1, 30.5, 29.2, 21.1, 18.6, 11.3 ppm. IR: v= 2945, 2868, 2181, 1618, 1497, 1250, 1009, 879, 662 ${\mathrm{{cm}}}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{21}{\mathrm{H}}_{31}\mathrm{{FSi}}$ : 330.2173; found: 330.2171.

((6-氟-1,2,3,4-四氢萘-1-基)乙炔基)三异丙基硅烷(30)。按照条件B制备标题化合物:无色油状物；产率45%(29.7毫克)。通过使用大赛璐手性帕克2xOD-H柱的HPLC分析测定ee值，条件:正己烷/异丙醇=100:0，0.5毫升/分钟，220纳米；t(主要)$= {16.9}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.1}\mathrm{\;{min}},{66}\%$ ee；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {3.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR(400兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta \; = {7.48} - {7.43}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.88} - {6.81}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.77} - {6.73}(\mathrm{\;m}$，1H)，3.80 - 3.75(m，1H)，2.86 - 2.68(m，2H)，2.16 - 2.09 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{2.03} - {1.92}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{1.91} - {1.83}\left( {\mathrm{\;m},1\mathrm{H}}\right)$，1.78 - 1.68(m，1H)，1.07 - 1.03(m，21H)；${}^{13}\mathrm{C}$ NMR(100兆赫，CDC1s)δ = 162.5，160.1，138.1，138.0，132.05，132.02，130.5，130.4，115.1，114.9，113.0，112.7，111.4，81.3，32.1，30.5，29.2，21.1，18.6，11.3 ppm。IR:v = 2945，2868，2181，1618，1497，1250，1009，879，662 ${\mathrm{{cm}}}^{-1}$；HRMS(EI):$m/z$计算得到${\left\lbrack \mathrm{M}\right\rbrack }^{ + }{\mathrm{C}}_{21}{\mathrm{H}}_{31}\mathrm{{FSi}}$:330.2173；实测值:330.2171。

((6-Chloro-1,2,3,4-tetrahydronaphthalen-1-yl)eth

((6-氯-1,2,3,4-四氢萘-1-基)乙炔

ynyl)triisopropylsilane (3p). The title compound was prepared according to condition B: Colorless oil; yield 75% (52.1 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: n-hexane/i-PrOH = 100:0, 0.5 mL/min, 220 nm; t (major) $= {16.9}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.4}\mathrm{\;{min}},{67}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {4.2}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; = {7.42}\left( {\mathrm{\;d},\mathrm{\;J} = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.11}\left( {\mathrm{\;{dd}}, J = {2.4},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${7.04}\left( {\mathrm{\;d}, J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.79} - {3.74}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.82} - {2.68} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{2.15} - {2.08}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.03} - {1.92}\left( {\mathrm{\;m},1\mathrm{H}}\right)$ , 1.91-1.83 (m, 1H), 1.78-1.68 (m, 1H), 1.09-1.01 (m, 21H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {137.9},{134.9}$ , 131.8, 130.4, 128.6, 126.0, 111.0, 81.5, 32.1, 30.4, 29.0, 21.1,18.6,11.2; IR: $v = {2979},{2902},{2178},{1396},{1269}$ , 1056,904,870,786,675 ${\mathrm{{cm}}}^{-1}$ ; HRMS (EI): $m/z$ calcd for ${\left\lbrack \mathrm{M} - {\mathrm{C}}_{3}{\mathrm{H}}_{7}\right\rbrack }^{ + }{\mathrm{C}}_{18}{\mathrm{H}}_{24}\mathrm{{ClSi}} : {303.1330}$ ; found:303.1328.

(3p)三异丙基硅烷。标题化合物按照条件B制备:无色油状物；产率75%(52.1毫克)。对映体过量值通过使用大赛璐手性派克2xOD - H柱的HPLC分析测定，条件为:正己烷/异丙醇 = 100:0，0.5毫升/分钟，220纳米；t(主要)$= {16.9}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) = {16.4}\mathrm{\;{min}},{67}\%$ 对映体过量值；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {4.2}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ 核磁共振 $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; = {7.42}\left( {\mathrm{\;d},\mathrm{\;J} = {7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.11}\left( {\mathrm{\;{dd}}, J = {2.4},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ ， ${7.04}\left( {\mathrm{\;d}, J = {2.0}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.79} - {3.74}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.82} - {2.68} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{2.15} - {2.08}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.03} - {1.92}\left( {\mathrm{\;m},1\mathrm{H}}\right)$ ，1.91 - 1.83(m，1H)，1.78 - 1.68(m，1H)，1.09 - 1.01(m，21H)；${}^{13}\mathrm{C}$ 核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta = {137.9},{134.9}$ ，131.8，130.4，128.6，126.0，111.0，81.5，32.1，30.4，29.0，21.1，18.6，11.2；红外光谱:$v = {2979},{2902},{2178},{1396},{1269}$ ，1056，904，870，786，675 ${\mathrm{{cm}}}^{-1}$ ；高分辨质谱(电子轰击电离):$m/z$ 计算值为 ${\left\lbrack \mathrm{M} - {\mathrm{C}}_{3}{\mathrm{H}}_{7}\right\rbrack }^{ + }{\mathrm{C}}_{18}{\mathrm{H}}_{24}\mathrm{{ClSi}} : {303.1330}$ ；实测值:303.1328。

Triisopropyl((6-methoxy-1,2,3,4-tetrahydronaph-thalen-1-yl)ethynyl)silane (3q). The title compound was obtained according to condition B: Colorless oil; yield 70% (47.9 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, ${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ; t (major) $= {42.8}\mathrm{\;{min}},\mathrm{t}$ (minor) $= {38.2}\mathrm{\;{min}},{53}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {7.2}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; = {7.42}\left( {\mathrm{\;d},\mathrm{\;J} = {8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.72}\left( {\mathrm{\;{dd}}, J = {2.8},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${6.59}\left( {\mathrm{\;d}, J = {2.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.80} - {3.75}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{2.85} - {2.68} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{2.17} - {2.08}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.02} - {1.92}\left( {\mathrm{\;m},1\mathrm{H}}\right)$ , 1.90-1.81 (m, 1H), 1.78-1.65 (m, 1H), 1.09-1.03 (m, 21H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {158.0},{137.2}$ , 130.0, 128.6, 113.4, 112.0, 111.9, 80.7, 55.2, 31.9, 30.8, 29.4, 21.5, 18.6, 11.3; IR: v = 2932, 2908, 2131, 1565, 1510,1250,1049,817,752,666 cm ${}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}\mathrm{{OSi}} : {343.2451}$ ; found: 343.2450.

三异丙基((6-甲氧基-1,2,3,4-四氢萘-1-基)乙炔基)硅烷(3q)。根据条件B得到标题化合物:无色油状物；产率70%(47.9毫克)。通过使用大赛璐手性派克2xOD-H柱的HPLC分析测定对映体过量，条件:$n$ -己烷$/i$ -丙醇 = 100:0，${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$；t(主峰)$= {42.8}\mathrm{\;{min}},\mathrm{t}$(次峰)$= {38.2}\mathrm{\;{min}},{53}\%$对映体过量；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {7.2}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) \cdot {}^{1}\mathrm{H}$核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; = {7.42}\left( {\mathrm{\;d},\mathrm{\;J} = {8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{6.72}\left( {\mathrm{\;{dd}}, J = {2.8},{8.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，${6.59}\left( {\mathrm{\;d}, J = {2.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.80} - {3.75}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{2.85} - {2.68} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{2.17} - {2.08}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{2.02} - {1.92}\left( {\mathrm{\;m},1\mathrm{H}}\right)$，1.90 - 1.81(m，1H)，1.78 - 1.65(m，1H)，1.09 - 1.03(m，21H)；${}^{13}\mathrm{C}$核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta = {158.0},{137.2}$，130.0，128.6，113.4，112.0，111.9，80.7，55.2，31.9，30.8，29.4，21.5，18.6，11.3；红外光谱:v = 2932，2908，2131，1565，1510，1250，1049，817，752，666厘米${}^{-1}$；高分辨质谱(电喷雾电离):$m/z$计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}\mathrm{{OSi}} : {343.2451}$；实测值:343.2450。

Triisopropyl((5-methoxy-1,2,3,4-tetrahydronaph-thalen-1-yl)ethynyl)silane (3r). The title compound was prepared according to condition B: Colorless oil; yield 61% (41.7 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH $= {100} : 0,{0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$ ; $\mathrm{t}$ (major) $= {27.2}\mathrm{\;{min}},\mathrm{t}$ (minor) $= {21.4}\mathrm{\;{min}},{79}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {3.9}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) ;{}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta \; = {7.18} - {7.12}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{6.70}\left( {\mathrm{{dd}}, J = {1.6},{7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , 3.86-3.81 (m, 4H), 2.75-2.60 (m, 2H), 2.13-1.98 (m, 2H), 1.93-1.83 (m, 1H), 1.78-1.68 (m, 1H), 1.10-1.05 $\left( {\mathrm{m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {157.0},{137.5}$ , 125.9, 125.0, 121.2, 111.7, 107.5, 80.9, 55.2, 32.8, 30.2, 22.9,20.9,18.6,11.3; IR: $v = {2954},{2868},{2172},{1587}$ , 1467,1259,1009,882,792,678 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}\mathrm{{OSi}} : {343.2452}$ ; found: 343.2458.

三异丙基((5-甲氧基-1,2,3,4-四氢萘-1-基)乙炔基)硅烷(3r)。按照条件B制备标题化合物:无色油状物；产率61%(41.7毫克)。通过使用大赛璐手性派克2xOD-H柱的HPLC分析测定对映体过量，条件:$n$ -己烷$/i$ -丙醇$= {100} : 0,{0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}}$；$\mathrm{t}$(主要)$= {27.2}\mathrm{\;{min}},\mathrm{t}$(次要)$= {21.4}\mathrm{\;{min}},{79}\%$对映体过量；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} \; = + {3.9}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) ;{}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta \; = {7.18} - {7.12}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{6.70}\left( {\mathrm{{dd}}, J = {1.6},{7.2}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，3.86 - 3.81(m，4H)，2.75 - 2.60(m，2H)，2.13 - 1.98(m，2H)，1.93 - 1.83(m，1H)，1.78 - 1.68(m，1H)，1.10 - 1.05$\left( {\mathrm{m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {157.0},{137.5}$，125.9，125.0，121.2，111.7，107.5，80.9，55.2，32.8，30.2，22.9，20.9，18.6，11.3；红外光谱:$v = {2954},{2868},{2172},{1587}$，1467,1259,1009,882,792,678${\mathrm{{cm}}}^{-1}$；高分辨质谱(电喷雾电离):$m/z$计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{\mathrm{C}}_{22}{\mathrm{H}}_{35}\mathrm{{OSi}} : {343.2452}$；实测值:343.2458。

(Chroman-4-ylethynyl)triisopropylsilane (3s). The title compound was prepared according to condition B. Colorless oil; yield 41% (25.7 mg). The ee was determined by HPLC analysis using Daicel Chiralpak 2xOD-H column, conditions: $n$ -hexane $/i$ -PrOH = 100:0, ${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}};\mathrm{t}\left( \mathrm{{major}}\right) = {11.8}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) =$ 12.7 min,57% ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {6.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) ;{}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) $\delta = {7.38}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , 7.15-7.09 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{6.91} - {6.85}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.80} - {6.76}(\mathrm{\;m}$ , 1H), ${4.38} - {4.31}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{4.20} - {4.12}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{3.89}(\mathrm{t}, J = \; {6.4}\mathrm{\;{Hz}},1\mathrm{H}),{2.28} - {2.08}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.08} - {1.02}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ = 153.7, 129.7, 128.2, 121.9, 120.4, 116.8, 109.8, 82.1, 64.4, 29.3, 28.5, 18.6, 11.2; IR: $v = {2960},{2861},{2178},{1581},{1491},{1222},{1003},{882}$ , 752,663 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI): $m/z$ calcd for ${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{20}{\mathrm{H}}_{31}\mathrm{{OSi}}$ : 315.2139; found: 315.2145.

(苯并二氢吡喃-4-基乙炔基)三异丙基硅烷(3s)。标题化合物根据条件B制备。无色油状物；产率41%(25.7毫克)。对映体过量值通过使用大赛璐手性派克2xOD-H柱的HPLC分析测定，条件:$n$ -己烷$/i$ -丙醇 = 100:0，${0.5}\mathrm{\;{mL}}/\mathrm{{min}},{220}\mathrm{\;{nm}};\mathrm{t}\left( \mathrm{{major}}\right) = {11.8}\mathrm{\;{min}},\mathrm{t}\left( \mathrm{{minor}}\right) =$ 12.7分钟，57%对映体过量值；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = + {6.0}\left( {c = {0.2},{\mathrm{{CHCl}}}_{3}}\right) ;{}^{1}\mathrm{H}$核磁共振(400兆赫兹，CDCl3)$\delta = {7.38}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ ，7.15 - 7.09$\left( {\mathrm{m},1\mathrm{H}}\right) ,{6.91} - {6.85}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{6.80} - {6.76}(\mathrm{\;m}$ ，1H)，${4.38} - {4.31}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{4.20} - {4.12}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{3.89}(\mathrm{t}, J = \; {6.4}\mathrm{\;{Hz}},1\mathrm{H}),{2.28} - {2.08}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{1.08} - {1.02}\left( {\mathrm{\;m},{21}\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100兆赫兹，CDCl3)δ = 153.7，129.7，128.2，121.9，120.4，116.8，109.8，82.1，64.4，29.3，28.5，18.6，11.2；红外光谱:$v = {2960},{2861},{2178},{1581},{1491},{1222},{1003},{882}$ ，752,663${\mathrm{{cm}}}^{-1}$ ；高分辨质谱(电喷雾电离):$m/z$计算值为${\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + } \; {\mathrm{C}}_{20}{\mathrm{H}}_{31}\mathrm{{OSi}}$ :315.2139；实测值:315.2145。

Removal of the TIPS Group from 3f. The transformation was referred to the known procedure. ${}^{\left\lbrack {19}\right\rbrack }$ A 10-mL Schlenk tube was charged with the product 3f (75.2 mg,0.2 mmol) and THF (2 mL), and filled with nitrogen. To the solution cooled to $0{}^{ \circ }\mathrm{C}$ was added a solution of tetrabutylammonium fluoride (1.0 M solution in THF; 0.21 mL, 0.21 mmol) dropwise via syringe over 2 min. After $6\mathrm{\;h}$ , the reaction was quenched with water $\left( {2\mathrm{\;{mL}}}\right)$ . The layers were separated, and the aqueous layer was extracted with diethyl ether ( $3 \times {20}\mathrm{\;{mL}}$ ). The combined organic layers were washed with brine $\left( {{50}\mathrm{\;{mL}}}\right)$ , dried over ${\mathrm{{Na}}}_{2}{\mathrm{{SO}}}_{4}$ , filtered, and concentrated. Then the mixture was purified by silica gel column chromatography (eluted with petroleum ether) to afford the desilylation product 5 as oil (33.0mg, 75%). The ee was determined by HPLC analysis using Daicel Chi-ralpak OJ-H column, conditions: n-hexane/i-PrOH = 98:2, 1.0 mL/min, 220 nm; t (major) = 16.2 min, t (minor) $= {18.4}\mathrm{\;{min}};{75}\%$ ee; ${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = - {5.0}\left( {c = {1.0},{\mathrm{{CHCl}}}_{3}}\right)$ ; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta = {6.61}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{3.87}(\mathrm{\;s}$ , 6H), 3.83 (s, 3H), 3.70 (dq, J = 2.4, 7.2 Hz, 1H), 2.28 (d, $J = {2.4}\mathrm{\;{Hz}},1\mathrm{H}),{1.50}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {153.2},{138.3},{136.8},{103.9},{87.0}$ , 70.3,60.8,56.1,31.9,24.2 ppm. IR: $v = {2926},{2360}$ , 1587,1460,1064,820,743 ${\mathrm{{cm}}}^{-1}$ ; The absolute configuration (R) of 5 was established by the comparison of its optical rotation with the same compound of known configuration reported in the literature. ${}^{\left\lbrack {20}\right\rbrack }$

从3f中去除TIPS基团。该转化参考已知方法进行。${}^{\left\lbrack {19}\right\rbrack }$ 在一个10毫升的Schlenk管中加入产物3f(75.2毫克，0.2毫摩尔)和四氢呋喃(2毫升)，并充入氮气。向冷却至$0{}^{ \circ }\mathrm{C}$ 的溶液中通过注射器在2分钟内逐滴加入四丁基氟化铵溶液(1.0 M四氢呋喃溶液；0.21毫升，0.21毫摩尔)。$6\mathrm{\;h}$ 后，用水$\left( {2\mathrm{\;{mL}}}\right)$ 淬灭反应。分离各层，水层用乙醚($3 \times {20}\mathrm{\;{mL}}$ )萃取。合并的有机层用盐水$\left( {{50}\mathrm{\;{mL}}}\right)$ 洗涤，经${\mathrm{{Na}}}_{2}{\mathrm{{SO}}}_{4}$ 干燥，过滤并浓缩。然后通过硅胶柱色谱法(用石油醚洗脱)纯化混合物，得到脱硅产物5，为油状(33.0毫克，产率75%)。通过使用Daicel Chi-ralpak OJ-H柱的HPLC分析测定ee值，条件:正己烷/异丙醇 = 98:2，1.0毫升/分钟，220纳米；t(主峰) = 16.2分钟，t(次峰)$= {18.4}\mathrm{\;{min}};{75}\%$ ee；${\left\lbrack \alpha \right\rbrack }_{\mathrm{D}}^{20} = - {5.0}\left( {c = {1.0},{\mathrm{{CHCl}}}_{3}}\right)$ ；${}^{1}\mathrm{H}$ NMR(400兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta = {6.61}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{3.87}(\mathrm{\;s}$ ，6H)，3.83(单峰，3H)，3.70(二重四重峰，J = 2.4，7.2赫兹，1H)，2.28(双峰，$J = {2.4}\mathrm{\;{Hz}},1\mathrm{H}),{1.50}\left( {\mathrm{\;d}, J = {7.2}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta = {153.2},{138.3},{136.8},{103.9},{87.0}$ ，70.3、60.8、56.1、31.9、24.2 ppm。红外光谱:$v = {2926},{2360}$ ，1587、1460、1064、820、743 ${\mathrm{{cm}}}^{-1}$ ；通过将其旋光与文献中报道的相同构型的已知化合物进行比较，确定了5的绝对构型(R)。${}^{\left\lbrack {20}\right\rbrack }$

Results and Discussion

结果与讨论

We began our investigation by examining the Cu(I)-catalyzed cross-coupling reaction between triiso-propylsilylethyne 1 and $N$ -tosylhydrazones 2a (Table 1). Chiral phosphoramidite ligand 4a was used to compare the reactivity of various Cu catalysts. It was found that the reactions catalyzed by CuOAc, CuCl, CuBr, CuI, ${\mathrm{{CuCl}}}_{2},\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}$ and $\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{BF}}}_{4}$ all afforded the product $3\mathbf{a}$ in moderate yield (entries 1-7), however, $\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}$ gave the optimal enantioselectivity (83% ee). Next, base and solvent effects were examined. ${\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}$ and dioxane were identified as the best combination (entries 7-16). The ratio of the ligand $\mathbf{{4a}}$ to the $\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}$ was also investigated (entries 17,18). The results indicated that more than 2 equiv of the chiral ligand is required to obtain high enantioselectivity. Presumably one Cu(I) needs to coordinate with two phos-phoramidite ligands in order to achieve high selectivity. At last, the effect of ligand was studied in order to improve the enantioselectivity, however, the phospho-ramidite ligands $4\mathbf{b} - \mathbf{h}$ gave inferior results as compared with $4\mathbf{a}$ under the similar conditions (entries 7,19-25).

我们通过研究三异丙基甲硅烷基乙炔1与$N$ -对甲苯磺酰腙2a之间的铜(I)催化交叉偶联反应(表1)开始了我们的研究。使用手性亚磷酰胺配体4a来比较各种铜催化剂的反应活性。发现由醋酸铜、氯化铜、溴化铜、碘化铜、${\mathrm{{CuCl}}}_{2},\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}$和$\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{BF}}}_{4}$催化的反应均以中等产率得到产物$3\mathbf{a}$(条目1 - 7)，然而，$\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}$给出了最佳对映选择性(83% ee)。接下来，研究了碱和溶剂的影响。${\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}$和二氧六环被确定为最佳组合(条目7 - 16)。还研究了配体$\mathbf{{4a}}$与$\mathrm{{Cu}}{\left( \mathrm{{MeCN}}\right) }_{4}{\mathrm{{PF}}}_{6}$的比例(条目17,18)。结果表明，需要超过2当量的手性配体才能获得高对映选择性。据推测，一个铜(I)需要与两个亚磷酰胺配体配位才能实现高选择性。最后，为了提高对映选择性研究了配体的影响，然而，在相似条件下，与$4\mathbf{a}$相比，亚磷酰胺配体$4\mathbf{b} - \mathbf{h}$给出了较差的结果(条目7,19 - 25)。

With the optimal reaction conditions, the reaction scope was then evaluated. A series of $N$ -tosylhydrazones 2a-i (R = Me) bearing electron-neutral, -deficient or -rich aromatic substituents were smoothly reacted with triisopropylsilylethyne 1 to give the corresponding coupling product 3a-i in 55-83% ee and 40-80% yield (Scheme 2). ${}^{21}$ Compared with $N$ -tosylhydrazone 3c, increasing the alkyl chain length at R led to decreased ee (3j, 3k). The scope of the coupling reaction could also be extended to $N$ -tosylhydrazones derived from tetralone. The reactions of both 7- and 6-subsituted te-tralone-derived hydrazones (2I-q) proceeded with moderate to good yields and enantioselectivity (45-82% yield, 53-82% ee, 31-q). 5-Methoxyl-1-tetralone-derived hydrazone was a good substrate, and it readily reacted with triisopropylsilylethyne to deliver the products in 61% yield with 79% ee (3r). Finally, the chroma-none-derived hydrazone (2s) furnished alkyne product 3s in 41% yield and 57% ee.

在优化的反应条件下，然后评估了反应范围。一系列带有电子中性、缺电子或富电子芳基取代基的$N$ -对甲苯磺酰腙2a - i(R = 甲基)与三异丙基甲硅烷基乙炔1顺利反应，以55 - 83% ee和40 - 80%的产率得到相应的偶联产物3a - i(方案2)。${}^{21}$与$N$ -对甲苯磺酰腙3c相比，R处烷基链长度增加导致ee值降低(3j，3k)。偶联反应的范围也可以扩展到四氢萘酮衍生的$N$ -对甲苯磺酰腙。7 - 和6 - 取代的四氢萘酮衍生的腙(2I - q)的反应均以中等至良好的产率和对映选择性进行(产率45 - 82%，ee值53 - 82%，31 - q)。5 - 甲氧基 - 1 - 四氢萘酮衍生的腙是一种良好的底物，它很容易与三异丙基甲硅烷基乙炔反应，以61%的产率和79% ee得到产物(3r)。最后，色满酮衍生的腙(2s)以41%的产率和57% ee得到炔烃产物3s。

(1)

The products could be converted to a useful synthetic intermediate by removal of the TIPS group. Treatment of $3\mathbf{f}$ with tetrabutylammonium fluoride in THF (1.0 M) afforded the desilylated terminal alkyne 5 in 75% yield without noticeable loss of the ee value (eq 1). The absolute configuration $\left( R\right)$ of5was established by the comparison of its optical rotation with the same compound of known configuration reported in the literature. ${}^{\left\lbrack {20}\right\rbrack }$

通过去除TIPS基团，产物可以转化为有用的合成中间体。在四氢呋喃(1.0 M)中用四丁基氟化铵处理$3\mathbf{f}$得到去硅基化的末端炔烃5，产率为75%，ee值没有明显损失(方程式1)。通过将其旋光与文献中报道的相同构型的化合物进行比较，确定了5的绝对构型$\left( R\right)$。${}^{\left\lbrack {20}\right\rbrack }$

Table 1. Optimization of reaction conditions ${}^{a}$

表1. 反应条件的优化 ${}^{a}$

${}^{a}$ Reaction was run under the following conditions: a solution of $\mathbf{1}\left( {{0.2}\mathrm{{mmol}}}\right) ,\mathbf{{2a}}\left( {{0.3}\mathrm{{mmol}}}\right)$ , base $\left( {{0.6}\mathrm{{mmol}}}\right)$ , cat. [Cu] (5 mol%), and chiral ligand (12 mol%) in anhydrous solvent (2 mL) was stirred at ${70}^{ \circ }\mathrm{C}$ under nitrogen atmosphere for ${24}\mathrm{\;h} \cdot {}^{b}$ Yields refer to isolated products. ${}^{c}$ Determined by HPLC analysis using a chiral stationary phase. ${}^{d}$ Not determined. ${}^{e}5\mathrm{\;{mol}}\%$ chiral ligand $4\mathrm{a}$ was used. ${}^{f}6\mathrm{\;{mol}}\%$ chiral ligand $4\mathrm{a}$ was used. ${}^{g}$ The major enantiomer has opposite configuration.

${}^{a}$ 反应在以下条件下进行:将 $\mathbf{1}\left( {{0.2}\mathrm{{mmol}}}\right) ,\mathbf{{2a}}\left( {{0.3}\mathrm{{mmol}}}\right)$、碱 $\left( {{0.6}\mathrm{{mmol}}}\right)$、催化剂 [Cu](5 摩尔%)和手性配体(12 摩尔%)在无水溶剂(2 毫升)中的溶液在氮气气氛下于 ${70}^{ \circ }\mathrm{C}$ 搅拌 ${24}\mathrm{\;h} \cdot {}^{b}$。产率指分离得到的产物。${}^{c}$ 通过使用手性固定相的高效液相色谱分析测定。${}^{d}$ 未测定。${}^{e}5\mathrm{\;{mol}}\%$ 使用了手性配体 $4\mathrm{a}$。${}^{f}6\mathrm{\;{mol}}\%$ 使用了手性配体 $4\mathrm{a}$。${}^{g}$ 主要对映体具有相反的构型。

$3\mathrm{\;h}\mathrm{R} = \mathrm{H}{\left( {60}\% \text{ yield, }{79}\% \mathrm{{ee}}\right) }^{a}$ 3i $\mathrm{R} =$ OMe (50% yield, ${55}\% \mathrm{{ee}}{)}^{a}$

$3\mathrm{\;h}\mathrm{R} = \mathrm{H}{\left( {60}\% \text{ yield, }{79}\% \mathrm{{ee}}\right) }^{a}$ 3i $\mathrm{R} =$ OMe(产率50%，${55}\% \mathrm{{ee}}{)}^{a}$

31 R = H (80% yield, 82% ee)

31 R = H(产率80%，对映体过量82%)

3m R = Br (82% yield, 72% ee)

3m R = Br(产率82%，对映体过量72%)

3n R = Me (65% yield, 67% ee)

3n R = Me(产率65%，对映体过量67%)

doctor

医生

Scheme 2. Substrate scope for $N$ -tosylhydrazones

方案2. $N$ -甲苯磺酰腙的底物范围

3a $\mathrm{R} = m - \mathrm{{OMe}}{\left( {72}\% \text{ yield, }{83}\% \text{ ee }\right) }^{a}$

$3\mathrm{\;b}\mathrm{R} = \mathrm{H}{\left( {70}\% \text{ yield },{75}\% \text{ ee }\right) }^{a}$ (52% yield, 69% ee) ${}^{a}$

$3\mathrm{\;b}\mathrm{R} = \mathrm{H}{\left( {70}\% \text{ yield },{75}\% \text{ ee }\right) }^{a}$(产率52%，对映体过量69%)${}^{a}$

3c R = p-OMe (80% yield, 70% ee) ${}^{a}$

3c R = p - OMe(产率80%，对映体过量70%)${}^{a}$

$3\mathrm{\;d}\mathrm{R} = p - \mathrm{{Ph}}{\left( {40}\% \text{ yield, }{79}\% \mathrm{{ee}}\right) }^{a}$

3e $\mathrm{R} = p - \mathrm{{Br}}{\left( {74}\% \text{ yield, }{63}\% \mathrm{{ee}}\right) }^{a}$

3f $R = 3,4,5 - {\mathrm{{OMe}}}_{3}{\left( {45}\% \text{ yield, }{74}\% \mathrm{{ee}}\right) }^{a}$

3j 3k

(76% yield, 46% ee) (60% yield, 42% ee)

(产率76%，对映体过量达46%)(产率60%，对映体过量42%)

3o R = F (45% yield, 66% ee)

3o R = F(产率45%，对映体过量66%)

3p R = CI (75% yield, 67% ee)

3p R = CI(产率75%，对映体过量67%)

3q R = OMe (70% yield, 53% ee)

3q R = OMe(产率70%，对映体过量53%)

Si

3r

(61% yield, 79% ee) (41% yield, 57% ee) ${}^{a}$ Reaction conditions: a solution of $\mathbf{1}\left( {{0.2}\mathrm{{mmol}}}\right) ,\mathbf{2}\left( {{0.3}\mathrm{{mmol}}}\right) ,{\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}\left( {{0.6}\mathrm{{mmol}}}\right) ,\mathrm{{Cu}}\left( \mathrm{{MeCN}}\right) {}_{4}{\mathrm{{PF}}}_{6}\left( {5\mathrm{{mol}}\% }\right)$ , and 4a (12 mol%) in dioxane (2 mL) was stirred at ${70}^{ \circ }\mathrm{C}$ under nitrogen atmosphere for ${24}\mathrm{\;h}.{}^{b}{12}\mathrm{\;{mol}}\% \mathbf{{4f}}$ was used. The yields refer to isolated products. The ee values were determined by chiral HPLC analysis.

(61%产率，79%对映体过量) (41%产率，57%对映体过量) ${}^{a}$反应条件:在氮气气氛下，将$\mathbf{1}\left( {{0.2}\mathrm{{mmol}}}\right) ,\mathbf{2}\left( {{0.3}\mathrm{{mmol}}}\right) ,{\mathrm{{Cs}}}_{2}{\mathrm{{CO}}}_{3}\left( {{0.6}\mathrm{{mmol}}}\right) ,\mathrm{{Cu}}\left( \mathrm{{MeCN}}\right) {}_{4}{\mathrm{{PF}}}_{6}\left( {5\mathrm{{mol}}\% }\right)$和4a(12摩尔%)的二氧六环(2毫升)溶液在${70}^{ \circ }\mathrm{C}$搅拌${24}\mathrm{\;h}.{}^{b}{12}\mathrm{\;{mol}}\% \mathbf{{4f}}$。产率指分离得到的产物。对映体过量值通过手性高效液相色谱分析测定。

Conclusions

结论

In summary, we have reported the first enantioselec-tive Cu(I)-catalyzed C(sp)-C(sp ${}^{3}$ ) cross-coupling reaction between triisopropylsilylethyne and $N$ -tosylhydrazones with chiral phosphoramidite as the ligand. A series of synthetically interesting, functionalized alkynes were obtained with moderate to good enantioselectivities. This methodology provides an method to achieve catalytic asymmetric construction of $\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$ bonds. The results may further motivate the investigation of $N$ -tosylhydrazones in asymmetric catalysis.

总之，我们报道了首例以手性亚磷酰胺为配体，在铜(I)催化下三异丙基甲硅烷基乙炔与$N$-甲苯磺酰腙之间的对映选择性C(sp)-C(sp ${}^{3}$ )交叉偶联反应。以中等至良好的对映选择性得到了一系列具有合成意义的官能化炔烃。该方法提供了一种实现$\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$键催化不对称构建的方法。这些结果可能会进一步推动对$N$-甲苯磺酰腙在不对称催化中的研究。

Acknowledgement

致谢

The project is supported by the National Basic Research Program of China (973 Program, No. 2015CB856600), the Natural Science Foundation of China (Grant 21472004, 21332002) and the China Postdoctoral Science Foundation Funded Project (2015M580911).

本项目得到了中国国家基础研究计划(973计划，编号2015CB856600)、中国国家自然科学基金(项目批准号21472004、21332002)以及中国博士后科学基金资助项目(2015M580911)的支持。

References

参考文献

[1] (a) The Chemistry of Triple-Bonded Functional Groups; Ed. S. Patai, Wiley, New York, 1994. (b) Modern Acetylene Chemistry; Stang, P. J.; Diederich, F.; Eds.; VCH, Weinheim, Germany, 1995; (c) Liu, J.; Lam, J. W. Y.; Tang, B. Z. Chem. Rev. 2009, 109, 5799-5867.

[2] (a) Chinchilla, R.; Nájera, C. Chem. Rev. 2007, 107, 874-922. (b) Chinchilla, R.; Nájera, C. Chem. Soc. Rev. 2011, 40, 5084-5121. (c) Wang, D.; Gao, S. Org. Chem. Front. 2014, 1, 556-566. (d) Thomas, A. M.; Sujatha, A.; Anilkumar, G. RSC Adv. 2014, 4, 21688-21698. (e) Karak, M.; Barbosa, L. C. A.; Hargaden, G. C. RSC Adv. 2014, 4, 53442-53466.

[3] Eckhardt, M.; Fu, G. C. J. Am. Chem. Soc. 2013, 135, 3387-3390.

[4] (a) Altenhoff, G.; Würtz, S.; Glorius, F. Tetrahedron Lett. 2006, 47, 2925-2928. (b) Vechorkin, O.; Barmaz, D.; Proust, V.; Hu, X. J. Am. Chem. Soc. 2009, 131, 12078-12079. (c) Ano, Y.; Tobisu, M.; Chatani, N. J. Am. Chem. Soc. 2011, 133, 12984-12986. (d) Yi, J.; Lu, X.; Sun, Y.-Y.; Xiao, B.; Liu, L. Angew. Chem. Int. Ed. 2013, 52, 12409-12413. (e) He, J.; Wasa, M.; Chan, K. S. L.; Yu, J.-Q. J. Am. Chem. Soc. 2013, 135, 3387-3390. (f) García, P. M. P.; Ren, P.; Scopelliti, R.; Hu, X. ACS Catal. 2015, 5, 1164-1171; (g) Luo, F.-X.; Xu, X.; Wang, D.; Cao, Z.-C.; Zhang, Y.-F.; Shi, Z.-J. Org. Lett. 2016, 18, 2040-2043.

[5] (a) Schaffner, A.-P.; Darmency, V.; Renaud, P. Angew. Chem. Int. Ed. 2006, 45, 5847-5849. (b) Huang, H.; Zhang, G.; Gong, L.; Zhang, S.; Chen, Y. J. Am. Chem. Soc. 2014, 136, 2280-2283. (c) Xie, J.; Shi, S.; Zhang, T.; Mehrkens, N.; Rudolph, M.; Hashmi, A. S. K. Angew. Chem. Int. Ed. 2015, 54, 6046-6050. (d) Liu, W.; Li, L.; Li, C.-J. Nat. Commun. 2015, 6, 6526-6531.

[6] (a) Tang, S.; Wang, P.; Li, H.; Lei, A. Nat. Commun. 2016, 7, 11676-11683. (b) Luo, F.-X.; Cao, Z.-C.; Zhao, H.-W.; Wang, D.; Zhang, Y.-F.; Xu, X.; Shi, Z.-J. Organometallics 2017, 36, 18-21.

[7] (a) Rayabarapu, D. K.; Tunge, J. A. J. Am. Chem. Soc. 2005, 127, 13510-13511. (b) Bi, H.-P.; Zhao, L.; Liang, Y.-M.; Li, C.-J. Angew. Chem. Int. Ed. 2009, 48, 792-795. (c) Zhang, W.-W.; Zhang, X.-G.; Li, J.-H. J. Org. Chem. 2010, 75, 5259-5264. (d) Zhang, C.; Seidel, D. J. Am. Chem. Soc. 2010, 132, 1798-1799. (e) Liu, X.; Wang, Z.; Cheng, X.; Li, C. J. Am. Chem. Soc. 2012, 134, 14330-14333. (f) Feng, Y.-S.; Xu, Z.-Q.; Mao, L.; Zhang, F.-F.; Xu, H.-J. Org. Lett. 2013, 15, 1472-1475. (g) Vaillant, F. L.; Courant, T.; Waser, J. Angew. Chem. Int. Ed. 2015, 54, 11200-11204. (h) Zhang, H.; Zhang, P.; Jiang, M.; Yang, H.; Fu, H. Org. Lett. 2017, 19, 1016-1019.

[8] (a) Yang, L.-M.; Huang, L.-F.; Luh, T. -Y. Org. Lett. 2004, 6, 1461-1463. (b) Zhao, Y.; Wang, H.; Hou, X.; Hu, Y.; Lei, A.; Zhang, H.; Zhu, L. J. Am. Chem. Soc. 2006, 128, 15048-15049. (c) Ohmiya, H.; Yorimitsu, H.; Oshima, K. Org. Lett. 2006, 8, 3093-3096. (d) Cahiez, G.; Gager, O.; Buendia, J. Angew. Chem. Int. Ed. 2010, 49, 1278-1281. (e) Chen, M.; Zheng, X.; Li, W.; He, J.; Lei, A. J. Am. Chem. Soc. 2010, 132, 4101-4103. (f) Thaler, T.; Guo, L.-N.; Mayer, P.; Knochel, P. Angew. Chem. Int. Ed. 2011, 50, 2174-2177. (g) Hatakeyama, T.; Okada, Y.; Yoshimoto, Y.; Nakamura, M. Angew. Chem. Int. Ed. 2011, 50, 10973-10976. (h) Vechorkin, O.; Godinat, A.; Scopelliti, R.; Hu, X. Angew. Chem. Int. Ed. 2011, 50, 11777-11781. (i) Cheung, C.W.; Ren, P.; Hu, X. Org. Lett. 2014, 16, 2566-2569.

[9] Chirality transfer from enantiomerically enriched acetylides: Mendis, S. N.; Tunge, J. A. Org. Lett. 2015, 17, 5164-5167.

10 Caeiro, J.; Sestelo, J. P.; Sarandeses, L. A. Chem. Eur. J. 2008, 14, 741-746. (b) Fang, H.; Yang, Z.; Zhang, L.; Wang, W.; Li, Y.; Xu, X.; Zhou, S. Org. Lett. 2016, 18, 6022-6025.

[11]Chen, Z.-M.; Nervig, C. S.; DeLuca, R. J.; Sigman, M. S. Angew. Chem. Int. Ed. 2017, 56, 6651-6654.

[12]Ye, F.; Ma, X.; Xiao, Q.; Li, H.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2012, 134, 5742-5745.

13 Suárez, A.; Fu, G. C. Angew. Chem. Int. Ed. 2004, 43, 3580-3582. (b) Liu, C.-B.; Meng, W.; Li, F.; Wang, S.; Nie, J.; Ma, J.-A. Angew. Chem. Int. Ed. 2012, 51, 6227-6230.

14 Zhang, Y.; Wang, J. Eur. J. Org. Chem. 2011, 1015-1026. (b) Barluenga, J.; Valdés, C. Angew. Chem. Int. Ed. 2011, 50, 7486-7500. (c) Shao, Z.; Zhang, H. Chem. Soc. Rev. 2012, 41, 560-572. (d) Xia, Y.; Zhang, Y.; Wang, J. ACS Catal. 2013, 3, 2586-2598. (e) Liu, Z.; Wang, J. J. Org. Chem. 2013, 78, 10024-10030. (f) Xiao, Q.; Zhang, Y.; Wang, J. Acc. Chem. Res. 2013, 46, 236-247. (g) Hu, F.; Xia, Y.; Ma, C.; Zhang, Y.; Wang, J. Chem. Commun. 2015, 51, 7986-7995. (h) Jadhav, A. P.; Ray, D.; Rao, V. U. B.; Singh, R. P. Eur. J. Org. Chem. 2016, 2369-2382. (i) Xia, Y.; Wang, J. Chem. Soc. Rev. 2017, 46, 2306-2362.

[15] Mercier, A.; Yeo, W. C.; Chou, J.; Chaudhuri, P. D.; Bernardinelli, G.; Kündig, E. P. Chem. Commun. 2009, 45, 5227-5229.

[16] Rimkus, A.; Sewald, N. Org. Lett. 2003, 5, 79-80.

[17] Zhao, X.; Jing, J.; Lu, K.; Zhang, Y.; Wang, J. Chem. Commun. 2010, 46, 1724-1726.

[18] Feng, J.; Li, B.; He, Y.; Gu, Z. Angew. Chem. Int. Ed. 2016, 55, 2186-2190.

[19] Shirakura, M.; Suginome, M. Org. Lett. 2009, 11, 523-526.

[20] Smith, S. W.; Fu, G. C. J. Am. Chem. Soc. 2008, 130, 12645-12647.

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[21]The ee value of 3e could not be determined by HPLC analysis, so the triisopropylsilyl group was removed to determine the enanti-oselectivity.

[21]由于无法通过HPLC分析确定3e的对映体过量值，因此除去三异丙基硅基以确定对映选择性。

Entry for the Table of Contents

目录条目

Page No.

页码

Cu(I)-Catalyzed Asymmetric Cross-Coupling of N-Tosylhydrazones and Trialkylsilylethynes: Enantiose-lective Construction of C(sp)-C(sp3) Bonds

铜(I)催化的N-甲苯磺酰腙与三烷基甲硅烷基乙炔的不对称交叉偶联:对映选择性构建C(sp)-C(sp3)键

Wen-Dao Chu, Fangfang Guo, Lefei Yu, Junting Hong, Qianyi Liu, Fanyang Mo, Yan Zhang and Jianbo Wang*

朱文道、郭芳芳、余乐飞、洪钧婷、刘谦益、莫凡洋、张燕和王建波*

The first catalytic enantioselective $\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$ cross-coupling reaction between $N$ -tosylhydrazones and trialkylsilylethynes has been developed. With $\mathrm{{Cu}}\left( \mathrm{I}\right)$ salt and chiral phosphoramidite ligands, coupling products were obtained with moderate to good enantioselectivities (up to 83% ee).

首次开发了 $\mathrm{C}\left( \mathrm{{sp}}\right) - \mathrm{C}\left( {\mathrm{{sp}}}^{3}\right)$ 催化的 $N$ -甲苯磺酰腙与三烷基硅基乙炔之间的对映选择性交叉偶联反应。使用 $\mathrm{{Cu}}\left( \mathrm{I}\right)$ 盐和手性磷酰胺配体，可得到具有中等至良好对映选择性(ee 值高达 83%)的偶联产物。

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