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Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Copper(ii)-catalyzed enantioselective decarboxylative Mannich reaction coordinated by supramolecular organic amine
Yuanli Zhu1, Houting Wang1, Rui Liu1
1Shanghai Frontiers Science Center of Biomimetic Catalysis, Joint Laboratory of International Cooperation of Resource Chemistry of Ministry of Education, Shanghai Normal University Shanghai 200234 China.
Abstract:
Using supramolecular chiral cages to create a favorable chiral environment can effectively address the limitations of traditional metal asymmetric catalysis in controlling chiral catalytically active centers. However, achieving harmonious interactions among the molecular cage, the metal, and the substrate within the cavity remains a significant challenge. To overcome this, we have designed a pyridinium-modified, chiral-diamine-functionalized cage with a distinct bowl-shaped geometry. This structure features three quaternary ammonium linkers at the base and three chiral cyclohexanediamine units positioned at the rim. Acting as a supramolecular chiral ligand, the coordination of this cage with copper salts forms an optimal chiral environment that enables an efficient decarboxylative Mannich reaction between β-ketoacids and imines, yielding a broad range of chiral β-amino carbonyl compounds. Mechanistic studies and control experiments reveal that the coordinated Cu center is responsible for the substrate grabbing and preorganization within the cavity and the free NH group contributes to the enhanced enantioselectivity through hydrogen bonds, collaboratively enhancing the overall catalytic efficiency.
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