A Powerful Chiral Phosphoric Acid Catalyst for Enantioselective Mukaiyama-Mannich Reactions

被引：47
作者：
Zhou, Fengtao [1 ]
Yamamoto, Hisashi [1 ]
机构：
[1] Chubu Univ, Mol Catalyst Res Ctr, 1200 Matsumoto Cho, Kasugai, Aichi 4878501, Japan
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 31期
关键词：
asymmetric catalysis; Bronsted acids; chiral phosphoric acids; Mukaiyama-Mannich reactions; quaternary stereogenic centers; BOND-FORMING REACTIONS; ENOL SILYL ETHERS; BRONSTED ACID; ASYMMETRIC-SYNTHESIS; KINETIC RESOLUTION; AMINO-ALCOHOLS; ALDOL REACTION; DIELS-ALDER; ACTIVATION; DESIGN;
D O I：
10.1002/anie.201603929
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A new BINOL-derived chiral phosphoric acid bearing 2,4,6-trimethyl-3,5-dinitrophenyl substituents at the 3,3'-positions was developed. The utility of this chiral phosphoric acid is demonstrated by a highly enantioselective (ee up to >99%) and diastereoselective (syn/anti up to >99: 1) asymmetric Mukaiyama-Mannich reaction of imines with a wide range of ketene silyl acetals. Moreover, this method was successfully applied to the construction of vicinal tertiary and quaternary stereogenic centers with excellent diastereo- and enantioselectivity. Significantly, BINOL-derived N-triflyl phosphoramide constitutes a complementary catalyst system that allows the title reaction to be applied to more challenging imines without an N-(2-hydroxyphenyl) moiety.
引用
收藏
页码：8970 / 8974
页数：5
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