Catalytic Enantioselective Desymmetrization of meso-Cyclopropane Fused Cyclohexene-1,4-diones via Formal C(sp2)-H Alkylation

Ray, S and Mukherjee, S (2022) Catalytic Enantioselective Desymmetrization of meso-Cyclopropane Fused Cyclohexene-1,4-diones via Formal C(sp2)-H Alkylation. In: Synlett .

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Abstract

Bicyclo4.1.0heptane framework, consisting of cis-fused cyclopropane and cyclohexane rings, is found in several bioactive compounds. Given the symmetry of this core, catalytic desymmetrization can be considered as the most straightforward strategy for their enantioselective synthesis. Known desymmetrization reactions of meso-bicyclo4.1.0heptane derivatives proceed with the opening of the cyclopropane ring. We now report the first ring-retentive desymmetrization of a bicyclo4.1.0heptane derivative, namely meso-cyclopropane-fused cyclohexene-1,4-diones through formal C(sp2)-H alkylation using nitroalkane as the alkylating agent. This reaction is catalyzed by a dihydroquinine-derived bifunctional tertiary aminosquaramide and generates the products with up to 97:3 er. An application of this reaction is demonstrated by the first catalytic enantioselective synthesis of the natural product (-)-car-3-ene-2,5-dione. © 2022 Georg Thieme Verlag. All rights reserved.

Item Type:	Journal Article
Publication:	Synlett
Publisher:	Georg Thieme Verlag
Additional Information:	The copyright for this article belongs to Thieme.
Department/Centre:	Division of Chemical Sciences > Organic Chemistry
Date Deposited:	06 Sep 2022 07:05
Last Modified:	06 Sep 2022 07:05
URI:	https://eprints.iisc.ac.in/id/eprint/76483

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