Cobalt-Catalyzed Deaminative Amino- and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light

Alexander M Veatch; Shubin Liu; Erik J Alexanian

doi:10.1002/anie.202210772

Cobalt-Catalyzed Deaminative Amino- and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light

Angew Chem Int Ed Engl. 2022 Dec 12;61(50):e202210772. doi: 10.1002/anie.202210772. Epub 2022 Nov 10.

Authors

Alexander M Veatch¹, Shubin Liu^{1

2}, Erik J Alexanian¹

Affiliations

¹ Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA.
² Research Computing Center, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA.

Abstract

Catalytic carbonylations of aryl electrophiles via C(sp² )-N cleavage remains a significant challenge. Herein, we demonstrate an aminocarbonylation of aniline-derived trialkylammonium salts promoted by visible light with a simple cobalt catalyst. The reaction proceeds under mild conditions suitable for late-stage functionalization and is amenable to telescoped carbonylations directly from anilines. A range of alkylamines are successful partners, and alkoxycarbonylation is also demonstrated. Mechanistic studies and DFT calculations support a novel mechanism for catalytic carbonylations of aryl electrophiles involving a key visible light-induced carbonyl photodissociation.

Keywords: Amines; Carbonylation; Cobalt; Synthetic Methods; Visible Light.

Abstract

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