Neighboring Carbonyl Group Assisted Oxyacetoxylation of Propargylic Carboxylates with Retention of Chirality under Metal Free Condition

Abstract A metal‐free oxyacetoxylation method of primary, secondary and tertiary propargylic carboxylates with retention of chirality was presented. The reaction proceeds through the intramolecular nucleophilic attack of the neighboring carbonyl group on an alkynyliodonium intermediate. The process is general with broad substrate scope and is amenable for application to a variety of propargyl carboxylates including those obtained from natural products. Insight into the mechanistic pathway by isotopic labelling (using H 2 O 18 and D 2 O) and controlled experiments confirmed. magnified image