Benzylic C-H Esterification with Limiting C-H Substrate Enabled by Photochemical Redox Buffering of the Cu Catalyst

Dung L. Golden, Chaofeng Zhang, Si-Jie Chen, Aristidis Vasilopoulos, Ilia A. Guzei and Shannon S. Stahl*

*Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States, Email: stahlchem.wisc.edu

D. L. Golden, C. Zhang, S.-J. Chen, A. Vasilopoulos, I. A. Guzei, S. S. Stahl, J. Am. Chem. Soc., 2023, 145, 9434-9440.

DOI: 10.1021/jacs.3c01662

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Abstract

A Cu/2,2′-biquinoline catalyst mediates a benzylic C-H esterification with limiting C-H substrate. Blue-light irradiation promotes carboxylate-to-copper charge transfer, reducing resting-state Cu^II to Cu^I, which activates the peroxide to generate an alkoxyl radical hydrogen-atom-transfer species. This "photochemical redox buffering" sustains the activity of Cu catalysts in radical-relay reactions.

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Key Words

benzylic alcohols, benzoates, peroxides, photochemistry

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ID: J48-Y2023