Rearrangements in the halogenation of tetraalkylethylenes with N-halosuccinimides and tert-butyl hypochlorite

The reaction of N-halosuccinimides and Me3COCl with tetraalkylethylenes involves halo-cation addn. to the double bond in a fast reaction, followed by abstraction of an allylic proton, resulting in a double bond shift. Homoallylic halogenation occurs in tetraalkylethylenes which can not undergo a double bond shift; e.g., adamantylideneadamantane gave the 4--halo deriv. The title electrophilic halogenation is compared with the well-known radical-chain allylic halogenation of mono-, di-, and trialkylethylenes with the same reagents and the reaction of chlorine with olefins. The halogenations of tetraalkylethylenes are strongly reminiscent of the singlet oxygen ene-reaction. [on SciFinder (R)]