DABCO-promoted photocatalytic C-H functionalization of aldehydes.

Herein we present a direct application of DABCO, an inexpensive and broadly accessible organic base, as a hydrogen atom transfer (HAT) abstractor in a photocatalytic strategy for aldehyde C-H activation. The acyl radicals generated in this step were arylated with aryl bromides through a well stablished nickel cross-coupling methodology, leading to a variety of interesting aryl ketones in good yields. We also performed computational calculations to shine light in the HAT step energetics and determined an optimized geometry for the transition state, showing that the hydrogen atom transfer between aldehydes and DABCO is a mildly endergonic, yet sufficiently fast step. The same calculations were performed with quinuclidine, for comparison of both catalysts and the differences are discussed. Copyright © 2021, Maia da Silva Santos et al.

Citation

Bruno Maia da Silva Santos, Mariana Dos Santos Dupim, Cauê Paula de Souza, Thiago Messias Cardozo, Fernanda Gadini Finelli. DABCO-promoted photocatalytic C-H functionalization of aldehydes. Beilstein journal of organic chemistry. 2021;17:2959-2967

PMID: 35003372

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