Acylphosphonic acid esters phosphites

Dialkyl phosphites react with acyl halides such as lauroyl chloride to yield surface-active acid esters of acylphosphonic acid [84-87] see Eq. (40). 

The Michaelis-Arbuzov reaction has been applied to t/7.v(trialkylsilyl) phosphites, which, on reaction with aliphatic or aromatic acyl halides in Et2O or CgHg at room temperature, undergo the rearrangement in mild conditions to produce the valuable fczXtrialkylsilyl) 1-oxoalkyl- or 1-oxoarylphosphonates in good yields (50-77%, Scheme 7.6). - Free acylphosphonic acids are obtained by treatment of the trimethylsilyl) esters with EtOH or by exposure to air for several hours. 

Acylphosphonic acids and esters Monoacyl phosphites a-Hydroxyphosphonic acid esters... 

A useful approach for the preparation of chiral (3-aminophospho-nic acids from the naturally occurring a-amino acids has been reported.139 The overall scheme (Equation 3.4) involves formation of the phthalimide-acid halide from the starting a-amino acid followed by a Michaelis-Arbuzov reaction with triethyl phosphite to give the acylphosphonate. Complete reduction of the carbonyl group in three steps followed by hydrolysis of the ester and amide linkages provides the target material in very high yield without racemization (>99% ee). 

Reaction of a,j5-unsaturated aldehydes with diethyl trimethylsilyl phosphite was used for the synthesis of chain-lengthened esters. Alkylation of the a-silyloxy-j ,y-unsaturated phosphonate with lithium diisopropylamide (Ida) and an alkyl halide occurs at the y-position with migration of the double bond to the a,j9-position. The silyloxyenolate could isolated in this reaction. Acide-catalysed alcoholysis leads to the carboxylic ester through the acylphosphonate (equation 93) ". ... 

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