Functionalization of alkenes by polyfluorinated α,β-unsaturated sulphenyl chlorides: Dual reactivity of perfluoro-2-methyl-2-penten-3-yl sulphenyl chloride in reactions with activated olefins

Article abstract of DOI:10.1016/0022-1139(96)03425-2

A dual reactivity of perfluoro-2-methyl-2-penten-3-yl sulphenyl chloride (1) in reactions with alkenes is described. Whereas 1 interacts with 3,3-dimethyl-l-butene and styrene in nitromethane solution in the sulphenyl chloride form, reactions with olefins that have mobile hydrogen atoms in an allylic position (e.g. allyl-and p-methoxyallyl-benzenes) occur through the tautomeric thioketone form - 2-chloroper-fluoro-2-methylpentanethione-3 (3) - with the formation of products by ene rearrangement. Chlorotropism in the system 1 ? 3 in the presence of nucleophilic solvents or catalysts is responsible for the dual reactivity of 1 in the above reactions.