Dehydrative C-H/N-OH functionalizations in H₂O by ruthenium(II) catalysis: Subtle effect of carboxylate ligands and mechanistic insight

(Chemical Equation Presented) A ruthenium(II) complex derived from the electron-deficient aromatic carboxylic acid 3-(F₃C)C₆H₄CO₂H proved to be a highly efficient catalyst for dehydrative alkyne annulation by NH-free hydroxamic acids in water. The C-H/N-OH functionalization occurred with excellent positional selectivity as well as ample substrate scope, setting the stage for effective intermolecular alkenylations of hydroxamic acids. Detailed mechanistic studies were suggestive of a kinetically relevant C-H metalation by carboxylate assistance along with subsequent migratory alkyne insertion, reductive elimination, and intramolecular oxidative addition.