Triplet Energy Transfer Mechanism in Copper Photocatalytic N- and O-Methylation

Chemistry. 2024 Apr 16;30(22):e202400560. doi: 10.1002/chem.202400560. Epub 2024 Mar 1.

Abstract

Methylation reactions are chemically simple but challenging to perform under mild and non-toxic conditions. A photochemical energy transfer strategy was merged with copper catalysis to enable fast reaction times of minutes and broad applicability to N-heterocycles, (hetero-)aromatic carboxylic acids, and drug-like molecules in high yields and good functional group tolerance. Detailed mechanistic investigations, using kinetic analysis, aprotic MS, UV/Vis, and luminescence quenching experiments revealed a triplet-triplet energy transfer mechanism between hypervalent iodine(III) reagents and readily available photosensitizers.

Keywords: copper catalysis; energy transfer; hypervalent iodine; methylation; photocatalysis.