Ruthenium Catalyzed Selective α- and α,β-Deuteration of Alcohols Using D2O

Highly selective ruthenium catalyzed α-deuteration of primary alcohols and α,β-deuteration of secondary alcohols are achieved using deuterium oxide (D2O) as a source of deuterium and reaction solvent. Minimal loading of catalyst (Ru-macho), base (KO t Bu), and low temperature heating provided efficient selective deuteration of alcohols making the process practically attractive and environmentally benign. Mechanistic studies indicate the D–O­(D/R) bond activations by metal–ligand cooperation and intermediacy of carbonyl compounds resulting from dehydrogenation of alcohols.