Sequential In Situ -Formed Kukhtin-Ramirez Adduct and P(NMe 2 ) 3 -Catalyzed O -Phosphination of α-Dicarbonyls with P(O)-H.

O -Phosphination of α-dicarbonyls via sequential in situ formation of a Kukhtin-Ramirez adduct and a P(NMe 2 ) 3 -catalyzed process has been exploited for the synthesis of α-phosphoryloxy carbonyls. A range of P(O)-H derivatives, including diarylphosphine oxides, arylphosphinates, and phosphinates, are competent candidates to be introduced into the α-dicarbonyls in this transformation, and various α-phosphoryloxy carbonyls are obtained. This approach possesses advantages of mild conditions, simple operations, atom economy, high efficiency, and gram-scale synthesis, which make it promising in the synthesis toolbox.