Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity

Gogoi, R and Jindal, G (2024) Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity. In: ACS Catalysis, 14 (16). pp. 12351-12358.

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Abstract

DLPNO-CCSD(T) calculations are carried out to understand the distinctive chemoselectivity in a Rh(II)-catalyzed carbene insertion into a C(sp2)-H bond in unprotected phenols without preinstalled directing groups. As per the conventional rules of solvation and a separated ion pair in polar aprotic solvents like acetonitrile, the reaction should have resulted in an O-H insertion. However, our calculations reveal a transition state model that helps in overriding the innate chemoselectivity in acetonitrile. It involves an explicit participation of the added Cs2CO3 base, where the interaction between the phenoxide oxygen and Cs cation, but not as a metal-bound Cs phenoxide, is crucial for controlling the chemoselectivity. Our study will be helpful in developing further reactions with a broad catalyst, substrate, and solvent scope. © 2024 American Chemical Society

Item Type:	Journal Article
Publication:	ACS Catalysis
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to the publisher.
Keywords:	Cesium compounds; Organic solvents; Rhodium compounds; Solvation, Carbene insertion; CCSD; Chemo-selectivity; Directing groups; DLPNO-CCSD(T); H-bonds; Ion pairs; Ions solvation; Polar aprotic solvent; Transition state, Acetonitrile
Department/Centre:	Division of Chemical Sciences > Organic Chemistry
Date Deposited:	29 Aug 2024 06:48
Last Modified:	29 Aug 2024 06:48
URI:	http://eprints.iisc.ac.in/id/eprint/85965

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