Luo Na, Ao Yu-Fei, Wang De-Xian, Wang Qi-Qiang
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2021 Sep 13;60(38):20650-20655. doi: 10.1002/anie.202106509. Epub 2021 Jun 22.
Exploiting anion-π interactions in catalyst design is a fascinating direction to develop new and fundamental catalysis. For the appealing yet flexible π-face activation, can two or more π-acidic surfaces be manipulated for cooperative activation to achieve efficient transformation and particularly selectivity control is highly desirable. Here, we demonstrate a supramolecular π-catalysis strategy by establishing cooperative π-face activation in a confined electron-deficient cage cavity. The catalysts have a triazine based prism-like cage core and pendant chiral base sites. Only 2 mol % of cage catalyst efficiently catalyzed the decarboxylate Mannich reactions of sulfamate-headed cyclic aldimines and a series of malonic acid half thioesters in nearly quantitative yields and up to 97 % ee, enabling an unprecedent organocatalytic approach. The supramolecular π-cavity is essential in harnessing cooperative anion-π interactions for the efficient activation and excellent selectivity control.
在催化剂设计中利用阴离子-π相互作用是开发新型基础催化的一个引人入胜的方向。对于吸引人且灵活的π面活化，能否操控两个或更多的π酸性表面进行协同活化以实现高效转化，特别是选择性控制，这是非常值得期待的。在此，我们通过在受限的缺电子笼腔中建立协同π面活化，展示了一种超分子π催化策略。这些催化剂具有基于三嗪的棱柱状笼状核心和手性侧基位点。仅2 mol%的笼状催化剂就能高效催化氨基磺酸酯头基环亚胺与一系列丙二酸半硫酯的脱羧曼尼希反应，产率接近定量，对映体过量值高达97%，实现了一种前所未有的有机催化方法。超分子π腔对于利用协同阴离子-π相互作用实现高效活化和出色的选择性控制至关重要。
