Iodo-azide adducts of exocyclic alkenes; structure and solvolysis

Abstract

The addition of iodine(I) azide, generated from sodium azide–iodine(I) chloride in acetonitrile, to 3-methylene-5α-androstane (1) and to 1-methylene-4-t-butylcyclohexane (42) in the presence of oxygen is regioselective and gives adducts containing an iodomethyl group, but is not stereoselective. Under a nitrogen atmosphere adducts containing an azidomethyl group are obtained, which arise via a radical pathway. iodomethyl- and azidomethyl-groups are readily identified by ¹³C n.m.r. spectroscopy and this has been used to confirm the structures of the products of addition of iodine(I) azide to camphene (45). Migration of an azide group occurs during solvolysis of the iodo-azide adducts (6) and (7) from 3-methylene-5α-androstane.