Temperature-Dependent Direct Enantioconvergent Silylation of a Racemic Cyclic Allylic Phosphate by Copper(I)-Catalyzed Allylic Substitution

被引：25

作者：

Delvos, Lukas B. ^{[1
]}

Oestreich, Martin ^{[1
]}

机构：

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

来源：

SYNTHESIS-STUTTGART | 2015年 / 47卷 / 07期

关键词：

allylic substitution; copper; enantioselectivity; N-heterocyclic carbenes; silicon; NUCLEOPHILIC SILICON; MECHANISTIC INSIGHT; TRANSFORMATION; ACTIVATION; CARBONATES; SILANES; COMPLEX; STEREOCHEMISTRY; ALLYLSILANES; DERIVATIVES;

D O I：

10.1055/s-0034-1380157

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The near-quantitative transformation of a racemic cyclic allylic phosphate to a highly enantiomerically enriched allylic silane by allylic substitution with a silicon nucleophile is reported. The reaction is catalyzed by a chiral NHC-copper(I) complex. Experimental analysis revealed a rare case of a direct enantioconvergent transformation where the enantiomeric allylic phosphates converge to the same allylic silane by two distinctive S(N)2 pathways with opposite diastereofacial selectivity.

引用

页码：924 / 933

页数：10

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