Iodosulfenylation of olefins with sulfenamides in the presence of metal iodides

Reactions of arylsulfenamides, arylsulfenates, thiobisamines, and dithiobis amines with olefins in the presence of zinc, tin(II), tin(IV), antimony(III ), or magnesium iodides were investigated. In the case of cage olefins, the reactions afford mixtures of 1,2-iodosulfides and diiodides, the ratio bet ween which depends on the type of iodine-containing Lewis acid. Iodosulfide s were obtained in the highest yields in the reactions of cage olefins upon activation with zinc or tin(II) iodides. In the case of olefins prone to t he Wagner-Meerwein rearrangement (bicyclo[2.2.1]heptanes) or to the additio n-elimination reaction (camphene), the corresponding products formed. A rea ction mechanism is proposed.