Selection between Diastereomeric Kinetic vs Thermodynamic Carbonyl Binding Modes Enables Enantioselective Iridium-Catalyzed anti-(α-Aryl)allylation of Aqueous Fluoral Hydrate and Difluoroacetaldehyde Ethyl Hemiacetal

被引：24

作者：

Cabrera, James M. ^{[1
]}

Tauber, Johannes ^{[1
]}

Zhang, Wandi ^{[1
]}

Xiang, Ming ^{[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 | 2018年 / 140卷 / 30期

关键词：

ALDEHYDE OXIDATION LEVEL; ANTI-HOMOALLYLIC ALCOHOLS; ASYMMETRIC FLUORINATION; ALLYL ACETATE; TRIFLUOROMETHYLATION; DI; ADDITIONS; UMPOLUNG; MONO;

D O I：

10.1021/jacs.8b05725

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Enantioselectivity increases with increasing carbonyl electrophilicity in 2-propanol-mediated reductive couplings of aldehydes with branched aryl-substituted allylic acetates to form products of carbonyl anti-(alpha-aryl)allylation. This unusual phenomenon is caused by aldehyde coordination to diastereomeric kinetic vs thermodynamic carbonyl binding sites that deliver enantiomeric products. Exploiting this effect, anti-diastereo- and enantioselective (alpha-aryl)allylations of fluoral hydrate and difluoroacetaldehyde ethyl hemiacetal were developed.

引用

页码：9392 / 9395

页数：4

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