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

作者：Hao Guo, Lie‐Wei Zhang, Hao Zhou, Wei Meng, Yu‐Fei Ao, De‐Xian Wang, Qi‐Qiang Wang · 发表于：Angewandte Chemie International Edition · 年份：2019 · DOI：10.1002/anie.201910399 · 被引用次数：77 · 研究领域：Supramolecular Chemistry and Complexes、Metal-Organic Frameworks: Synthesis and Applications、Molecular Sensors and Ion Detection

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 nucleophilic attack of β-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.