Work

Unlocking Chromium Decarboxylative Ligand-to-Metal Charge Transfer: Efficient and Redox-Neutral Allylation of Aldehydes Using Carboxylic Acids

Year: 2025

Type: article

Abstract: Here, we report the light-induced decarboxylative ligand-to-metal charge transfer (LMCT) of Cr(III) carboxylate complexes and demonstrate its applicability toward stereoselective Nozaki-Hiyama-Kishi (NHK) allylation reactions. The critical design element of our reaction was identifying a bipyridyl ligand scaffold that enables a single Cr catalyst to facilitate both photolytic dissociation and aldehyde addition. This approach allows for the direct utilization of carboxylic acids and eliminates the need for external redox reagents. The broad utility of this protocol was demonstrated by the preparation of a variety of homoallylic alcohols in good yields and diastereoselectivities as well as the identification of advantageous retrosynthetic disconnections. Extensive studies supported the LMCT mechanism of this transformation, including the characterization of the catalytically active Cr-carboxylate species.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.5c04691

Authors: Supeng Wu, Ziqi Jiao, Alex T. Sung, Abigail B. Faulhaber, Nathan D. Schley, Alexander W. Schuppe

Institution: Vanderbilt University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Vanderbilt University, National Institutes of Health, National Institute of General Medical Sciences