66325-22-2

Upstream product

• 78-92-2 iso-butanol 
• 108-95-2 phenol 
• 78605-38-6 Diphenyl 2-oxo-3-oxazolinylphosphonate 
• 72305-35-2 diphenyl (4,6-dimethyl-2-pyrimidyl) phosphate 
• 449813-82-5 3-(diphenylphosphono)-2-(N-cyanoimino)thiazolidine 
• 681035-22-3 (2-oxo-5,5-diphenyl-oxazolidin-3-yl)-phosphonic acid diphenyl ester 
• 2524-64-3 chlorophosphoric acid diphenyl ester 

Relevant academic research and scientific papers

Substitution- and elimination-free phosphorylation of functionalized alcohols catalyzed by oxidomolybdenum tetrachloride

Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl4) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et3N). The new catalytic protocol can be applied to the chemoselective phosphorylations of primary, secondary and tertiary alcohols as well as the substitution-free phosphorylations of allylic, propargylic, and benzylic alcohols. Functionalized alcohols bearing acetonide, tetrahydropyranyl ether, tert-butyldimethylsilyl ether, or ester group are also amenable to the new catalytic protocol. The most difficult scenarios involve substitution-free phosphorylations of 1-phenylethanol and 1-(2-naphthyl)ethanol which can be effected in 95 and 90% yields, respectively. ESI-MS, IR, 1H, and 31P NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride-triethylamine adduct such as [(RO)Mo(O)Cl3-Et3N] to be responsible for the catalytic turnover.

Phosphorylation of alcohols with N-phosphoryl oxazolidinones employing copper(II) triflate catalysis

(Chemical Equation Presented) Phosphoryl transfer from N-phosphoryl 5,5-diphenyl oxazolidinone is efficiently catalyzed by copper(II) triflate. The utility of this method has been demonstrated in the phosphorylation of representative primary, secondary, tertiary, phenolic, and allylic alcohols. These reaction conditions are significantly milder than employing alkoxides and allow the phosphorylation of biologically relevant molecules.

N-Phosphoryl oxazolidinones as effective phosphorylating agents

A number of N-phosphoryl oxazolidinones have been prepared and evaluated, the best being 5,5-diphenyl oxazolidinones, the utility of which was demonstrated in the phosphorylation of a number of representative primary, secondary, tertiary, and phenolic alcohols.

3-Phosphono-2-(N-cyanoimino)thiazolidine derivatives, new phosphorylating agents for alcohols

We have developed new phosphorylating agents, 3-phosphono-2-(N-cyanoimino)-thiazolidine derivatives (3-phosphono-NCTs), which were readily synthesized by phosphorylation of NCT, and transformed primary and secondary alcohols into phosphates in good yield. The transfer of three kinds of dialkylphosphono groups [(PhO)2P(O)-, (EtO)2P(O)-, (Cl3CCH2O)2P(O)-] proceeded in excellent yields. Selective phosphorylation of various alcohols was also accomplished.

Reaction of pyrimidyl esters of some phosphorus acids with isomeric butyl alcohols

A series of pyrimidyl esters of some phosphorus acids was prepared with the purpose of investigation of their reaction with isomeric butyl alcohols. According to31P NMR data, the obtained phosphates all are capable of phosphorylating isomeric butyl alcohols. The reactions with diphenyl (4-oxo-3,4-dihydro-2-pyrimidyl) phosphate and diphenyl (2-pyrimidyl) phosphate occur in quantitative yield under mild conditions, and the reactions with diphenyl (4,6-dimethyl-2-pyrimidyl) phosphate and dibutyl (4,6-dimethyl-2-pyrimidyl) phosphate require severe conditions to occur. In the latter two cases, certain reaction selectivity was observed, depending on the nature of the solvent and some other factors. Pyrimidyl esters of sulfur-containing phosphorus acids do not react with isomeric butyl alcohols under the studied conditions.

NEW PHOSPHORYLATING AGENTS FOR GENERAL SYNTHESIS OF MIXED PHOSPHATE ESTERS

An effective procedure has been developed for the general synthesis of mixed alkyl or aryl phosphate esters by metal-catalyzed phosphorylation of alcohols with aryl bis(2-oxo-3-oxazolinyl)phosphinate.Among metallic acetylacetonates examined as catalysts, the zirconium complex was the most effective as in activity order of Zr(IV)> Ce(III)> Zn(II)> Mn(III)> Mn(II)-complexes.