Rhodium(I)-catalyzed enantioselective 1,4-addition of nucleophilic silicon

被引：63

作者：

Walter, Christian ^{[1
]}

Froehlich, Roland ^{[1
]}

Oestreich, Martin ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

TETRAHEDRON | 2009年 / 65卷 / 28期

关键词：

Asymmetric catalysis; Boron; Conjugate addition; Homogeneous catalysis; Rhodium; Silicon; CATALYZED ASYMMETRIC 1,4-ADDITION; ALPHA; BETA-UNSATURATED CARBONYL-COMPOUNDS; CONJUGATE SILYL TRANSFER; BETA-UNSATURATED ESTERS; N-ENOYL-SULTAMS; CHIRAL AUXILIARIES; ADDITION-REACTIONS; HETEROATOM BONDS; HYDROXY KETONES; 1,4-DISILYLATION;

D O I：

10.1016/j.tet.2009.01.111

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A rhodium(I)-catalyzed activation of a silicon-boron linkage, that is, the transmetalation of silicon from boron to rhodium(I) by means of an Rh-1-OH complex, enables the conjugate transfer of nucleophilic silicon onto alpha,beta-unsaturated acceptors. Pre- or in situ formed cationic rhodium(I)-binap complexes catalyze this novel carbon-silicon bond formation with exceptional enantiocontrol, 92 to >99% ee for cyclic carbonyl and carboxyl Compounds as well as >99% ee for acyclic carboxyl compounds. (C) 2009 Elsevier Ltd. All rights reserved.

引用

页码：5513 / 5520

页数：8

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