Electrophilic Addition of Arylsulfenyl Chlorides to Tricyclo2,5>deca-3,7-diene and -3,7,9-triene Systems. Novel Skeletal Rearrangements and Serendipitous Products

Article abstract of DOI:10.1021/jo00339a003

The addition of 2-nitro- and 2,4-dinitrobenzenesulfenyl chlorides in AcOH and under "doping conditions" (AcOH + LiClO4) to the olefins 8-10 has been investigated, and novel types of Wagner-Meerwein rearrangement have been found.The product distributions as well as the different configurations of rearranged chlorides (e.g., 18c) and acetates (e.g., 18d) were explained in terms of an ion-pair mechanism.Doping addition leads in part to the formation of covalent perchlorates (e.g., 12d,e), which have been isolated and identified.The general mechanistic features and stereochemical sequence for the ion-pair mechanism of ArSCl addition to a carbon-carbon double bond are discussed.