Regio- and Diastereoselective Copper(I)-Catalyzed Allylic Substitution of δ-Hydroxy Allylic Chlorides by a Silicon Nucleophile

被引：27

作者：

Hazra, Chinmoy K. ^{[1
,2
]}

Irran, Elisabeth ^{[1
]}

Oestreich, Martin ^{[1
]}

机构：

[1] Tech Univ Berlin, Inst Chem, D-10623 Berlin, Germany

[2] Univ Munster, NRW Grad Sch Chem, Inst Organ Chem, D-48149 Munster, Germany

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2013年 / 2013卷 / 22期

关键词：

Allylic substitution; Copper; Diastereoselectivity; Regioselectivity; Silicon; Synthetic methods; FORMAL ALPHA-HYDROXYALLYLATION; B BOND ACTIVATION; STEREOCONTROLLED SYNTHESIS; ASYMMETRIC-SYNTHESIS; ENANTIOSELECTIVE SYNTHESIS; STEREOSELECTIVE SYNTHESIS; BETA-HYDROXYALLYLSILANES; CLAISEN REARRANGEMENTS; CHIRAL ALLYLSILANES; ORGANIC-SYNTHESIS;

D O I：

10.1002/ejoc.201300493

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A perfectly gamma-selective copper(I)-catalyzed allylic substitution of protected delta-hydroxy allylic chlorides with a silicon nucleophile generated by Si-B bond activation provides diastereoselective access to beta-hydroxy alpha-chiral allylic silanes with an anti relative configuration. The high levels of diastereocontrol of this rare allylic displacement are interpreted according to a model suggested by Nakamura where diastereofacial selectivity originates from steric control rather than an oxygen-directing effect in the Felkin-Anh transition state.

引用

页码：4903 / 4908

页数：6

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