Abstract
EtAlClj catalyzes the ene reactions of -substituted acrylate esters with trans 1,2-di- and trisubstituted alkenes at 25 eC. The reactions are regio- and stereoselective. The ester group adds endo and a hydrogen is transferred selectively from the alkyl group syn to the vinylic hydrogen. Methyl -chloroacrylate, -bromoacrylate, acetamidoacrylate, and methacrylate, ethyl α-bromomethylacrylate, and dimethyl itaconate were explored. Ene reactions of phenylmenthyi'a-bromoacrylate give a 3:1 mixture of diastereomers, indicating the potential for asymmetric induction in intermolecular ene reactions.