Trimethylphosphite, reaction+carbonyls

The bidentate formate ligand of OsH(K2-02CH)(CO)(P,Pr3)2 is converted into a monodentate group by carbonylation. Thus, the reaction of this compound with carbon monoxide gives 0sH K1-0C(0)H (C0)2(P Pr3)2. Similarly, the addition of a stoichiometric amount of trimethylphosphite yields 0sH k -0C(0)H (C0) P(OMe)3 (P Pr3)2, and the addition of a stoichiometric amount of ethyne di-carboxylic methyl ester leads to 0sH K1-0C(0)H (C0)(r 2-Me02CC=CC02Me) (P Pr3)2, which in solution partially dissociates the alkyne. As is shown in... 

Tris(trimethylsilyl)phosphites, analogous to trialkylphosphites, undergo Perkow reaction with a-halo carbonyl compounds to give vinyl phosphates.223 Reaction of a-chloroketone 19 with trimethylphosphite produces dimethyl enol phosphate 20, which is further converted to b is [trimethyls ilyl] esters 21 using MeaSiBr. 21 is also produced directly from a-chloroketone 19 on reacting with P(SiMe3)3. 

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