Catalytic asymmetric conjugate addition and allylic alkylation with Grignard reagents

被引：617

作者：

Harutyunyan, Syuzanna R. ^{[1
]}

den Hartog, Tim ^{[1
]}

Geurts, Koen ^{[1
]}

Minnaard, Adriaan J. ^{[1
]}

Feringa, Ben L. ^{[1
]}

机构：

[1] Univ Groningen, Fac Math & Nat Sci, Stratingh Inst Chem, Organ Chem Labs, NL-9747 AG Groningen, Netherlands

来源：

CHEMICAL REVIEWS | 2008年 / 108卷 / 08期

关键词：

D O I：

10.1021/cr068424k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The asymmetric conjugate addition and allylic alkylation using Grignard reagents have been reviewed. Reportedly, major advancements are realized in enantioselective conjugate addition and allylic substitution using Grignard reagents in the presence of chiral copper complexes. Noteworthy of these breakthroughs are the addition of simple alkyl Grignard reagents to acyclic enones and thioesters with excellent levels of stereocontrol and the generation of quaternary centers via conjugate addition of Grignard reagents. In addition to this is the potential use of MeMgBr as a hard carbon nucleophile to generate chiral allylic products that are considered as highly versatile chiral synthons. Lastly, the development of iterative catalytic protocols to generate acyclic structures with arrays of multiple stereocenters offers opportunities in complex natural product synthesis as demonstrated in emerging field of lipidomics.

引用

页码：2824 / 2852

页数：29

共 274 条

[81] REGIO AND STEREOSPECIFIC SYNTHESIS OF CIS-3-METHYL-6-METHYLETHYL AND TRANS-3-METHYL-6-METHYLETHYL CYCLOHEXENES AND 3-METHYL-4-METHYLETHYLCYCLOHEXENES - REACTIONS OF ALLYLIC ACETATES AND CARBAMATES WITH LI2CU3ME5 AND LICUME2 [J].