Substrate-Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

被引：58

作者：

Guo, Hao ^{[1
,2
]}

Zhang, Lie-Wei ^{[1
,2
]}

Zhou, Hao ^{[1
,2
]}

Meng, Wei ^{[1
]}

Ao, Yu-Fei ^{[1
]}

Wang, De-Xian ^{[1
,2
]}

Wang, Qi-Qiang ^{[1
,2
]}

机构：

[1] Chinese Acad Sci, Inst Chem, CAS Key Lab Mol Recognit & Funct, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China

[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 07期

基金：

中国国家自然科学基金;

关键词：

anion binding; chiral macrocycles; cooperative asymmetric catalysis; self-assembly; supramolecular catalysis; DECARBOXYLATIVE MANNICH REACTION; CYCLIC IMINES; RECOGNITION; THIOUREAS; KETOACIDS; KETONES; UREA;

D O I：

10.1002/anie.201910399

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An artificial system of substrate-induced dimerization assembly of chiral macrocycle catalysts enables a highly cooperative hydrogen-bonding activation network for efficient enantioselective transformation. These macrocycles contain two thiourea and two chiral diamine moieties and dimerize with sulfate to form a sandwich-like assembly. The macrocycles then adopt an extended conformation and reciprocally complement the hydrogen-bonding interaction sites. Inspired by the guest-induced dynamic assembly, these macrocycles catalyze the decarboxylative Mannich reaction of cyclic aldimines containing a sulfamate heading group. The imine substrate can be activated toward nudeophilic attack of beta-ketoacid by a cooperative hydrogen-bonding network enabled by sulfamate-induced dimerization assembly of the macrocycle catalysts. Highly efficient (> 95 % yield in most cases) and enantioselective (up to 97.5:2.5 er) transformation of a variety of substrates using only 5 mol % macrocycle was achieved.

引用

页码：2623 / 2627

页数：5

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