Phosphoric thiol esters

Following the same procedure, phosphoric thiol esters are prepared by the treatment of trialkylphosphites with thiols in the presence of TeCl4 and lutidine. ... 

In the particular case of the synthesis of the 14-member i polyoxomacrolide narbonolide, direct cyclization through the activation of thiol ester failed and then the mixed phosphoric anhydride derived from diphenylphosphorochloridate was developed to effect cyclization by Masamune and coworkers [39]. Fukumoto et al. [40] applied this procedure to the synthesis of the macrocyclic alkaloid vertaline 63). Thus, seco acid 62 was treated with diphenyl phosphorochloridate and triethylamine followed by refluxing in benzene in the presence of DMAP at high dilution afforded 63 in 54% yield (Scheme 20). 

The thiol ester intermediate resulting from oxidation of glyceraldehyde 3-phosphate next reacts with phosphate ion in a nucleophilic acyl substitution step (Section 21.2) to yield 3-phosphoglyceroyl phosphate, a mixed anhydride between a carboxylic acid and phosphoric acid. 

Esterases a large group of hydrolases acting on ester bonds R CXTOR -f HjO - R COOH-r R OH. The acid may be a carboxylic acid, phosphoric or sulfuric acid. The ester may be an alcoholic or a thiol ester. 

Optically active phosphorus(iii) acid esters PhR P (OR ) have recently been prepared for the first time by the reaction of a chiral phosphorus chloride and an alcohol or thiol in the presence of an optically active amine, in this case (-)-NN-dimethyl-(l-phenylethyl)amine. (See also Refs. 449 and 450). A kinetic investigation shows that phosphorous acid and chloral react to give 2,2,2-trichloro-l-hydroxyethyl phosphonate at a much lower rate than the corresponding reaction with dimethyl hydrogen phosphite. Phosphorus trichloride and dialkyl phosphites (R0)2P(0)H have been shown to react at low temperature in the presence of pyridine, producing tris(dialkoxyphosphoryl)phosphines [(RO)2P(0)]3P. ... 

An alcohol can react with phosphoric acid to produce a phosphate ester iphosphoester). When two phosphate groups are joined, the resulting bond is a phosphoric anhydride bond. These two functional groups are important to the structure and fimction o( adenosine triphosphate (ATP), the universal energy currency of all cells. Cellular enzymes can carry out a reaction between a thiol and a carboxylic acid to produce a thioester. This reaction is essential for the activation of acyl groups in carbohydrate and fatty acid metabolism. Coenz)une A is the most important thiol involved in these pathways. 

Organophosphate pesticides are synthetic and are usually esters, amides, or thiol derivatives of phosphoric, phosphonic, phosphorothioic, or phosphonothioic acids. Over 100 organo phosphorus compounds, representing a variety of chemical, physical, and biological properties, are currently on the market (Table 23.1). 

A wide range of 4-thio-substituted 2-aryl-4H-chromenes is formed when 2-hydroxychalcone derivatives react with various thiols (Scheme 27). Two new C-S and C-O bonds are formed in this catalyst-free domino reaction (13T2430). Chiral phosphoric acids catalyze the photocyclization reduction of 2-hydroxychalcones (13CEJ13658) and the 1,4-reduction of racemic 2,4-diaryl-2H-chromen-2-ols (13CEJ9775), both in the presence of the Hantzsch ester, to provide 2,4-diaryl-4H-chromenes in good yields and with excellent enantioselectivity. 

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