Synthesis of Phosphane Oxides and Phosphonates by Cerium-Mediated Addition of Organolithium Compounds to Chloro-Phosphorus Compounds

The addition of organocerium reagents 2a-g to phosphinoyl chloride 1a or chlorophosphates 1b leads to the synthesis of phosphane oxides 3aa-ag and phosphonates 3bb, be in good to high yield. The reaction can be extended to cerium enolates 4 (of ketones) and 6 (of nitriles) except when a benzyl group bound to the carbonyl moiety should be metallated. The latter reaction is the first reported synthesis of beta-oxophosphane oxides by a simple reaction between enolates and a phosphorus(V) halide.