Highly Selective Phosphinylphosphination of Alkenes with Tetraphenyldiphosphine Monoxide

Abstract

Abstract In sharp contrast to tetraphenyldiphosphine, which does not add to carbon–carbon double bonds efficiently, its monoxide, [Ph 2 P(O)PPh 2 ] can engage in a radical addition to various alkenes, thus affording the corresponding 1‐phosphinyl‐2‐phosphinoalkanes regioselectively, and they can be converted into their sulfides by treatment with elemental sulfur. The phosphinylphosphination proceeds by the homolytic cleavage of the P V (O)−P III single bond of Ph 2 P(O)PPh 2 , followed by selective attack of the phosphinyl radical at the terminal position of the alkenes, and selective trapping of the resulting carbon radical by the phosphino group. Furthermore, the phosphinylphosphination product could be converted directly into its platinum complex with a hemilabile P,O chelation.