Dialkyl phosphites review

For reviews of the Michaelis-Becker reaction, see Refs 6,13,14, and 59 the latter is one of a series of five reviews by Troev on the structure and reactions of dialkyl phosphites.59-63... 

Asymmetric addition of phosphorus compounds to C-N double bonds has been widely studied and mainly concerns the synthesis of chiral a-aminophosphonic acids (for reviews on the synthesis of aminophosphonic acids, see refs 36, 37 and 67). For this purpose, the following types of organic nitrogen compounds have been used aldimines and cyclic imines, nitrones, ureidoimino derivatives and imidothioloesters. A separate example is the addition of dialkyl phosphites to hydrazones, which was used for the synthesis of phosphonosugars. 

Michaelis-Becker reactions between sodium dialkyl phosphites and halogenated alkenes, seem to occur only with polyhalogenated alkenes, but the course of the reaction is then complicated by elimination and addition steps. Thus sodium dialkyl phosphites and 1,1,2-trichlorophenylethene react to give, ultimately, esters of (1-phenyl-1,2,2-ethane)trisphosphonic acid. Such reactions have been reviewed. ... 

Numerous synthetic applications of this reaction have been already reviewed in the early literature [353]. The Michaehs-Becker reaction takes place as a bimolecular nucleophilic substitution [354]. Direct evidence supporting the Sj 2 mechanism of this process is provided by the detected inversion of the configuration at the a-carbon atom of the alkyl halide in the product of the reaction between sodium diethyl phosphonate and methane-sulfonates (mesitylates) [355]. On the other hand, it has been established for related phos-phoryl compounds that they do not change the configuration at the phosphoras atom in the course of the Michaehs-Becker reaction [356-360]. One of the specifics of this process is the possibility of both 0-, and P- alkylation occuring as a result of the ambient character of the dialkyl phosphite anion. 

Dialkyl acylphosphonates were obtained for the first time by Kabachnik and Rossiiskaya in 1945 by the reaction of acyl chlorides with trialkyl phosphites. The reaction proceeds readily at room temperature and even on cooling by slowly adding trialkyl phosphite to acyl chlorides. Improvements have been made, especially by controlling the temperature of the reaction. The different versions of this reaction, which are distinguished by the nature of the acylating agent and the structure of the phosphite, have been covered by the reviews of Zhdanov et al. in 1980, Breuer in 1996," and McKenna and Kashemirov in 2002. ... 

The estimation of phosphorus by g.l.c. has been reviewed. Cyclic phosphites, phosphonates, and phosphates have been analysed by g.l.c. The zinc, gold, and cadmium chelates of dialkyl dithiophosphinates (235 ... 

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