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Updated: Aug 8, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Exploiting Vinylogy in Iminium-Catalyzed Desymmetrization of Cyclohexadienones
Abhijeet Singh1, Dhyanesh Kumar1, Imran Reja Mondal1
1Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi110016, India.
Abstract:
Desymmetrization of cyclohexadienones via a vinylogous Michael reaction, promoted by a cinchona alkaloid derived 9-amine catalyst, has been developed. The reaction proceeds through the iminium activation and leverages intermolecular addition, where a nucleophile attacks the β-position of the enone system, breaking the molecular symmetry with high enantioselectivity. The reaction led to a coumarin-derived 3,4-disubstituted cyclohexyl skeleton with the creation of two contiguous chiral centers in good yield with high stereocontrol. The asymmetric desymmetrization displays a broad substrate scope, stereodivergence, and diverse postsynthetic modification without erosion in selectivity.
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