Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes

Kadam, GA and Singha, T and Rawat, S and Hari, DP (2024) Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes. In: ACS Catalysis, 14 . pp. 12225-12233.

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Abstract

Skipped dienes are not only present in fatty acid primary metabolites and natural products but also serve as reactive intermediates in diverse chemical synthesis. Despite this, the regioselective and stereoselective synthesis of skipped dienes remains a challenging goal. Strain release in organic molecules is a powerful tool for creating chemical complexity under mild conditions. The reactivity of strained bicyclo1.1.0butane (BCB) systems is mainly dominated by transformations relying on their innate electrophilic reactivity. Herein, we report a rare example of the carbene-type reactivity of the BCB system based on rhodium-carbene chemistry, which enables the highly stereoselective synthesis of skipped dienes through strain release. The reaction is compatible with a diverse range of functional groups on both diazo compounds and BCBs and could be applied successfully to complex structures, providing highly valuable and functionalizable skipped dienes. The functional groups introduced during the reaction served as synthetic handles for downstream manipulations. The high stereoselectivity observed has been rationalized based on DFT calculations, which suggests that the reaction is likely proceeding via a concerted mechanism, and noncovalent interactions between the metallocarbene and BCB mainly control the observed exclusive selectivity. © 2024 American Chemical Society.

Item Type:	Journal Article
Publication:	ACS Catalysis
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Ions; Metabolites; Olefins; Rhodium compounds; Stereoselectivity, Bicyclobutane; Diazo compounds; Metallocarbene; Natural products; Primary metabolite; Reactive intermediate; Regioselective synthesis; Skipped diene; Stereoselective synthesis; Strain release, Fatty acids
Department/Centre:	Division of Chemical Sciences > Organic Chemistry
Date Deposited:	09 Sep 2024 10:01
Last Modified:	09 Sep 2024 10:01
URI:	http://eprints.iisc.ac.in/id/eprint/86025

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