Copper-Catalyzed trans-Hydroboration of Terminal Aryl Alkynes: Stereodivergent Synthesis of Alkenylboron Compounds

被引：113

作者：

Jang, Won Jun

Lee, Woo Lim

Moon, Jong Hun

Lee, Jin Yong ^{[1
]}

Yun, Jaesook ^{[1
]}

机构：

[1] Sungkyunkwan Univ, Dept Chem, Suwon 440746, South Korea

来源：

ORGANIC LETTERS | 2016年 / 18卷 / 06期

基金：

新加坡国家研究基金会;

关键词：

SELECTIVE HYDROBORATION; FORMAL HYDROBORATION; CONVENIENT SYNTHESIS; STRYKERS REAGENT; HYDROSILYLATION; RUTHENIUM; ESTERS; REGIO; HYDROSILATION; MECHANISM;

D O I：

10.1021/acs.orglett.6b00325

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A Cu-catalyzed highly Z-stereoselective hydroboration of alkynes with 1,8-naphthalenediaminatoborane (HB(dan)) is developed. DPEphos (bis[(2-diphenylphosphino)phenyl] ether)-ligated Cu catalysts produced alkenylboron compounds from terminal alkynes with excellent Z-stereoselectivity. In contrast, using a SIPr-CuCl complex as the precatalyst exclusively produced E-hydroboration products at mild conditions. Both catalytic procedures form alkenylboron products stereocomplementary to each other, constituting stereodivergent hydroboration of alkynes through Cu catalysis. Deuterium labeling and isomerization studies support the Z-selective hydroboration via trans-addition of the boron reagent to terminal alkynes as opposed to precedent noble-metal-catalyzed trans-hydroboration.

引用

收藏

页码：1390 / 1393

页数：4

相关论文

共 42 条

[1] (BDP)CuH: A "hot" Stryker's reagent for use in achiral conjugate reductions [J].

Baker, Benjamin A. ;

Bokovic, Zarko V. ;

Lipshutz, Bruce H. .

ORGANIC LETTERS, 2008, 10 (02) :289-292

[2] Recent developments in alkyne borylations [J].

Barbeyron, Renaud ;

Benedetti, Erica ;

Cossy, Janine ;

Vasseur, Jean-Jacques ;

Arseniyadis, Stellios ;

Smietana, Michael .

TETRAHEDRON, 2014, 70 (45) :8431-8452

[3] Hydroborations catalysed by transition metal complexes [J].

Beletskaya, I ;

Pelter, A .

TETRAHEDRON, 1997, 53 (14) :4957-5026

[4] CATECHOLBORANE (1,3,2-BENZODIOXABOROLE) AS A NEW, GENERAL MONOHYDROBORATION REAGENT FOR ALKYNES - CONVENIENT SYNTHESIS OF ALKENEBORONIC ESTERS AND ACIDS FROM ALKYNES VIA HYDROBORATION [J].

BROWN, HC ;

GUPTA, SK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (12) :4370-&

[5] A theoretical study on the mechanism, regiochemistry, and stereochemistry of hydrosilylation catalyzed by cationic ruthenium complexes [J].

Chung, LW ;

Wu, YD ;

Trost, BM ;

Ball, ZT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (38) :11578-11582

[6] Catalytic Non-Conventional trans-Hydroboration: A Theoretical and Experimental Perspective [J].

Cid, Jessica ;

Carbo, Jorge J. ;

Fernandez, Elena .

CHEMISTRY-A EUROPEAN JOURNAL, 2012, 18 (05) :1512-1521

[7]

Davidson M.G., 2000, CONT BORON CHEM

[8] Asymmetric Reductive Mannich Reaction to Ketimines Catalyzed by a Cu(I) Complex [J].

Du, Yao ;

Xu, Li-Wen ;

Shimizu, Yohei ;

Oisaki, Kounosuke ;

Kanai, Motomu ;

Shibasaki, Masakatsu .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (48) :16146-+

[9] Regio- and Enantioselective Copper(I)-Catalyzed Hydroboration of Borylalkenes: Asymmetric Synthesis of 1,1-Diborylalkanes [J].

Feng, Xinhui ;

Jeon, Heekyung ;

Yun, Jaesook .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (14) :3989-3992

[10] Regioselective transformation of alkynes catalyzed by a copper hydride or boryl copper species [J].

Fujihara, Tetsuaki ;

Semba, Kazuhiko ;

Terao, Jun ;

Tsuji, Yasushi .

CATALYSIS SCIENCE & TECHNOLOGY, 2014, 4 (06) :1699-1709

← 1 2 3 4 5 →