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
收藏
页码：3655 / 3658
页数：4
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