A New Route to Vinyl Phosphorus Derivatives by Formal Insertion of Phosphinidenes into the Carbon−Chlorine Bond of Chloroalkenes

Abstract

The reaction of a transient terminal phosphinidene complex such as [PhP−W(CO)5] with chloroalkenes yields (phenyl)(vinyl)chlorophosphine complexes formally resulting from an insertion of the phosphorus unit into the C−Cl bond with retention of the alkene stereochemistry. The mechanism involves intermediate phosphirane complexes in which a concerted migration of chlorine takes place from carbon to phosphorus. Oxidative decomplexation yields the corresponding (phenyl)(vinyl)phosphinates.