Light-Driven Enantioselective Organocatalytic β-Benzylation of Enals

被引：55

作者：

Dell'Amico, Luca ^{[3
]}

Fernandez-Alvarez, Victor M. ^{[3
]}

Maseras, Feliu ^{[2
,3
]}

Melchiorre, Paolo ^{[1
,3
]}

机构：

[1] Catalan Inst Res & Adv Studies, ICREA, Passeig Lluis Co 23, Barcelona 08010, Spain

[2] Univ Autonoma Barcelona, Dept Quim, Bellaterra 08193, Spain

[3] ICIQ, Inst Chem Res Catalonia, Barcelona Inst Sci & Technol, Ave Paisos Catalans 16, Tarragona 43007, Spain

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 12期

基金：

欧洲研究理事会;

关键词：

asymmetric catalysis; benzylation; organocatalysis; photochemistry; synthetic methods; HYDROXY-O-QUINODIMETHANES; CONJUGATE ADDITION; CATALYSIS; 2-METHYLBENZOPHENONE; MECHANISMS; HAMIGERANS;

D O I：

10.1002/anie.201612159

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A photochemical organocatalytic strategy for the direct enantioselective beta-benzylation of alpha,beta-unsaturated aldehydes is reported. The chemistry capitalizes upon the light-triggered enolization of 2-alkyl-benzophenones to afford hydroxy-o-quinodinomethanes. These fleeting intermediates are stereoselectively intercepted by chiral iminium ions, transiently formed upon condensation of a secondary amine catalyst with enals. Density functional theory (DFT) studies provided an explanation for why the reaction proceeds through an unconventional Michael-type addition manifold, instead of a classical cycloaddition mechanism and subsequent ring-opening.

引用

页码：3304 / 3308

页数：5

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