Addition of arenesulphenyl chlorides to 2-methylenebicyclo[2.2.1]hept-5-ene: effect of increasing electron demand upon the rate and product determining transition states

Abstract

The rates and products of addition of a series of sixteen arenesulphenyl chlorides to 2-methylenebicyclo[2.2.1]hept-5-ene, 7, and the E, Z isomeric 2-ethylidenebicyclo[2.2.1]hept-5-enes, 8 and 9, have been determined in methylene chloride solution. The major species from attack on 7 is always endo-3-arylthio-1-chloromethyltricyclo[2.2.1.02,6]heptane, the product of exo attack upon the endocyclic double bond with homoallylic participation of the exocyclic π system. No evidence was found for initial electrophilic attack upon the exocyclic double bond.