Iodosobenzene-Mediated α-Acyloxylation of 1,3-Dicarbonyl Compounds with Carboxylic Acids and Insight into the Reaction Mechanism.

Abstract

A highly efficient direct α-acyloxylation of 1,3-dicarbonyl compounds with carboxylic acids mediated by hypervalent iodine reagent is presented. Treatment of a variety of 1,3-dicarbonyl compounds with carboxylic acids in the presence of iodosobenzene provides the corresponding α-acyloxylated products in good to excellent yields. The mechanistic investigation by means of NMR spectroscopy reveals that the in situ-generated phenyliodine biscarboxylate proves to be the key intermediate for the α-acyloxylation, and the loading sequence of reactants and oxidant is crucial for the generation of the active species. The mild reaction conditions, wide substrate scope, short reaction time, good yields, high chemoselectivity, excellent functional group tolerance, and metal catalyst-free conversion make this acyloxylation a significant synthetic protocol.