Substrate-Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis
Substrate-Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis
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手性大环催化剂的底物诱导二聚组装实现协同不对称催化
DOI：
10.1002/anie.201910399
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发表时间：
2020-02-10
影响因子：
16.6
通讯作者：
Wang, Qi-Qiang
中科院分区：
文献类型：
--
作者：
Guo, Hao;Zhang, Lie-Wei;Wang, Qi-Qiang
手性大环催化剂的底物诱导二聚组装的人工系统能够形成高度协作的氢键活化网络，从而实现有效的对映选择性转化。这些大环化合物含有两个硫脲和两个手性二胺部分，并与硫酸盐二聚形成三明治状组装体。然后大环采用扩展构象并相互补充氢键相互作用位点。受客体诱导的动态组装的启发，这些大环化合物催化含有氨基磺酸盐标题基团的环状醛亚胺的脱羧曼尼希反应。亚胺底物可以通过由氨基磺酸诱导的大环催化剂的二聚组装实现的协同氢键网络而被活化以针对β-酮酸的亲核攻击。仅使用 5 mol% 大环化合物即可实现多种底物的高效（大多数情况下产率 > 95%）和对映选择性（高达 97.5:2.5 er）转化。
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.