DMF as Carbon Source: Rh-Catalyzed α‑Methylation of Ketones

An unprecedented Rh-catalyzed direct methylation of ketones with <i>N</i>,<i>N</i>-dimethyl­formamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.