INSERTION OF CARBENES INTO P-H BONDS. 5. SYNTHESIS OF NEW PHOSPHONATES AND PHOSPHINATES IN REACTIONS CATALYSED BY Cu,Pd,Rh,Ni COMPLEXES

Cu(OTf) 2 and Cu(acac) 2 were found to be the most effective catalysts in the reaction of diazo compounds Ph 2 CN 2 (1a), EtOC(O)CHN 2 (1b), MeOC(O)CHN 2 (1c), MeC(O)CN 2 C(O)OMe (1d), Cl-CH 2 C(O)CHN 2 (1e) and CH 2 N 2 (1f) with hydrophosphoryl compounds (MeO) 2 P(O)H (2a), (t-BuO) 2 P(O)H (2b), Ph(MeO)P(O)H (2c), (EtO) 2 P(O)H (2d) and P(O)H (2e) resulting in P-C bond formations. Cu, Pd and Rh acetates and Ni(acac) 2 have a much lower efficiency. Chlorines in Cl 3 CC(O)CH 2 P(O)(OMe) 2 (3k) and Cl 2 CHC(O)CH 2 P(O)(OMe) 2 (3l) are reduced in the copper catalysed Atherton-Todd reaction.