A new preparation of P-keto phosphonates from a-bromo ketones, by reaction of dialkyl chlorophosphate electrophiles with the dilithiated derivative of the bromo ketone, is described. This umpolung approach is complementary to the classical Arbuzov synthesis in two important ways. It extends the range of possible ketone substrates, allowing use of secondary a-halo ketones or a-bromo ketones where the Arbuzov reaction often fails. It ...