LAUSR

Terminal acetals were synthesized from various vinylarenes and 1,2‐ or 1,3‐diols using a simple PdCl2(MeCN)2/methoxy‐p‐benzoquinone (MeOBQ)/CuCl catalyst system and 1 atm of O2 under mild reaction conditions by the anti‐Markovnikov nucleophilic attack of an oxygen nucleophile on the coordinated vinylarenes. Cyclic α,β‐unsaturated carbonyl compounds such as MeOBQ and N‐phenylmaleimide were especially effective as additives to afford higher yields of the desired terminal acetals. Kinetic experiments indicated that MeOBQ operates as a π‐acceptor ligand for Pd to accelerate the reaction and that the dissociation of a chloride ion from Pd precedes the rate‐determining step.