Enantioselective Copper(I)-Catalyzed Alkynylation of Oxocarbenium Ions to Set Diaryl Tetrasubstituted Stereocenters

被引：60

作者：

Dasgupta, Srimoyee ^{[1
]}

Rivas, Thomas ^{[1
]}

Watson, Mary P. ^{[1
]}

机构：

[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 47期

基金：

美国国家科学基金会;

关键词：

alkynes; asymmetric catalysis; enantioselectivity; oxocarbenium ion; oxygen heterocycles; CATALYTIC ASYMMETRIC-SYNTHESIS; COPPER(I) COMPLEXES; KETONES; ETHERS; TRANSFORMATION; REDUCTION; ACETYLIDE; DINUCLEAR; ALDEHYDES; ADDITIONS;

D O I：

10.1002/anie.201507373

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An enantioselective, copper(I)-catalyzed addition of terminal alkynes to isochroman ketals to set diaryl, tetrasubstituted stereocenters has been developed. The success of this reaction relies on identification of a Cu/PyBox catalyst capable of distinguishing the faces of the diaryl-substituted oxocarbenium ion. This challenging transformation enables efficient conversion of readily available, racemic ketals into high-value enantioenriched isochroman products with fully substituted stereogenic centers. High yields and enantiomeric excesses are observed for various isochroman ketals and an array of alkynes.

引用

页码：14154 / 14158

页数：5

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