Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination

被引：47

作者：

Garza, Victoria J. ^{[1
]}

Krische, Michael J. ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 11期

关键词：

ALDEHYDE OXIDATION LEVEL; ASYMMETRIC ALPHA-HYDROXYMETHYLATION; C BOND FORMATION; AQUEOUS FORMALDEHYDE; ALDOL REACTION; HOMOALLYL ALCOHOLS; LEWIS-ACIDS; ALLYLATION; ALLYLBORATION; RUTHENIUM;

D O I：

10.1021/jacs.6b01078

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic pi-facial discrimination of sigma-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition.

引用

页码：3655 / 3658

页数：4

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