Direct methylation of organohalides represents a valuable but challenging transformation, typically requiring harsh reaction conditions or reagents. We report a radical approach for the methylation of (hetero)aryl chlorides using metallaphotoredox catalysis wherein trimethyl orthoformate, a common laboratory solvent, serves as a methyl source. This method permits methylation of (hetero)aryl chlorides and acyl chlorides at an early and late-stage with broad functional group compatibility. Mechanistic investigations indicate that trimethyl orthoformate serves as a source for methyl radical via beta-scission upon chlorine-mediated hydrogen atom transfer.

Methylation of (hetero)aryl chlorides via halogen photoelimination

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.