Phosphinates, Perkow reaction

The reaction of aldehydes with carbon tetrachloride in the presence of excess tris(dimethylamino)phosphine has been used to prepare vinyl dihalides in yields of 50—70%. It is suggested that the reaction takes place via an intermediate salt (77), although the formation of this salt seems more likely to be analogous to the Perkow reaction than to involve attack on oxygen. 

Hoffmann, H. and Diehr, H.J., Reaction of tertiary phosphines on a-halocarbonyl compounds. Model experiment on the Perkow reaction. Tetrahedron Lett., 3, 583, 1962. 

Perkow reaction of ketone (16) with P(OEt>3 and P(OEt)Ph2 afforded the vinyl phosphate 17 and vinyl phosphinate 18, respectively.21... 

Many of the reactions applied to the synthesis of phosphonoyl and phosphinoyl alkanoic acids described in the previous section can also, in principle, be applied to the synthesis of oxoalkyl-phosphonic and -phosphinic acids. A notable exception, however, is the synthesis of those compounds in which the oxo group is in the j5-position relative to phosphorus, when important syntheses lead not to phosphonate or phosphinate esters, but rather to enol esters of phosphoric acid through what is now referred to as the Perkow reaction ... 

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