Diethyl Phosphorochloridate phosphorylation

When the monosodium salts of uracil and similar pyrimidines react with diphenyl phosphorochloridate, phosphorylation takes place on oxygen unless other suitable nucleophilic centres are present and free.69 The reaction between the sodium salt of a 1,3-dicarbonyl compound and diethyl phosphorochloridothionate yields the Z-vinylphosphorothionate if the tetrabutylammonium salt is employed, the product has E geometry. This phenomenon has been interpreted in terms of the shape of the... 

Phosphate groups can also be removed by dissolving-metal reduction. Reductive removal of vinyl phosphate groups is one of the better methods for conversion of a carbonyl compound to an alkene.150 151 The required vinyl phosphate esters are obtained by phosphorylation of the enolate with diethyl phosphorochloridate or NJ, N, N -tetra-methyldiamidophosphorochloridate.152 153... 

In preparation for the eventual removal of the undesired oxygen function at C-10 of 313 via a Birch reduction, the phenol 313 was phosphorylated with diethyl phosphorochloridate in the presence of triethylamine to give 314, which underwent stereoselective reduction with sodium borohydride with concomitant N-deacylation to deliver the amino alcohol 315. N-Methylation of 315 by the Eschweiler-Clarke protocol using formaldehyde and formic acid followed by ammonolysis of the ester group and acetylation of the C-2 hydroxyl function afforded 316. Dehydration of the amide moiety in 316 with phosphorus oxychloride and subsequent reaction of the resulting amino nitrile 317 with LiAlH4 furnished 318, which underwent reduction with sodium in liquid ammonia to provide unnatural (+)-galanthamine. 

A synthetic approach to /3-sultams containing a direct bond between a tri- or tetracoordinated phosphorus atom and the nitrogen atom of the 1,2-thiazetidine 1,1-dioxide ring has been realized by direct phosphitylation or phosphorylation at nitrogen. Unfortunately, attempts to synthesize N-phosphorylated /3-sultams by reaction with diethyl phosphorochloridate and diethyl phosphorobromidate, generated in situ from diethyl phosphate and carbon tetrachloride or carbon tetrabromide, failed. However, when the /3-sultam is treated with freshly distilled diethyl phosphorochloridite or tetramethylphosphorodiamidous chloride in the presence of triethylamine, the expected AHliethy I phosphite and iV-phosphorodiamidous /3-sultams 150 are obtained (Equation 10). /3-Sultams unsubstituted... 

According to the original process of Addor (1962), phospholan is prepared by the reaction of ethylene-1,2-dithiol with cyanogen chloride, followed by the reaction of 2-imino-l,3-dithiolane (103) with diethyl phosphorochloridate. According to his later process (1970), N-(0,0-diethylphosphoryl) dithiocarbamate (104), obtained by the addition reaction of diethyl phosphoryl isothiocyanate and potassium hydrosulilde, is cyclised with ethylene bromide. 

Enone 69 is converted to the less substituted alkene 71 via the intermediacy of the enol phosphate 70.4 The sequence shown involves reduction with Li/NH3 (liquid) followed by phosphorylation of the resulting lithium enolates with diethyl phosphorochloridate to give 70, which is then treated with Li/EtNIVf-BuOH. Application of such methodology to steroid conversion has been reported by Ireland and Pfister41 and Kanata et al. 2... 

The successful C-phosphorylation of aliphatic nitro compounds with a free a-hydrogen has been reported. The treatment of nitroethane or 1-nitropropane with 2 equiv. of Ida in thf, followed by the addition of diethyl phosphorochloridate, yields the diethyl (1-nitroalkyl)phosphonates (Et0)2P(0)CHRN02 (R = Me or Et) ". The failure of such a reaction to occur with smaller amounts of BuLi had been noted some years earlier, but the later success seems not to have been followed through with any more detailed and extensive examination. 

A new phosphorylating reagent, dibenzyl phosphorofluoridate, has been introduced. In the presence of caesium fluoride as base it reacts with primary and anomeric hydroxy groups preferentially. Secondary hydroxy groups, e.q.. those of partially protected myo-inositol, can be phosphorylated after deprotection with butyl lithium. 1,2-Di-phosphates were obtained in good to excellent yields by treatment of vicinal diols with diethyl phosphorochloridate and butyl lithium there was no evidence of formation of cyclic phosphates, the predominant products when other bases are used. Q-Glycosylation of phosphonic and phosphinic acids has been achieved by the trichloroacetimidate method examples are given in Scheme 4. ... 

Phosphorylation. Diethyl phosphorochloridate is highly electrophilic and can be cleanly reacted at an anionic center provided that prior metalation is regio- and chemoselective. For example, phenols, thiophenols, and anilines can be phosphorylated under basic conditions (eq 1). The phosphorylated compound can be isolated, or treated further with bases, resulting in orthomet-alation followed by a facile 1,3-phosphorus migration from the heteroatom to carbon. If carbon phosphorylation is desired, simply treating thiophenol with 2 equiv of n-Butyllithium followed by diethyl phosphorochloridate gave a moderate yield (58%). ... 

Di-3,5-dinitrophenyl phosphate is hydrolyzed to orthophosphate, and benzyl 3,5-dinitrophenyl phosphate to benzyl phosphate [26], upon UV irradiation. Also, adenosine has been phosphorylated with di-3,5-dinitrophenyl phosphorochloridate and the two protecting groups removed by irradiation to yield adenosine 5 -phosphate. The photo-initiated hydrolysis is accompanied by almost complete P—0, as opposed to C—O, bond fission. Similarly 3-nitrophenol has been used as a protecting group for the synthesis of the highly reactive Pi, Pi-diethyl pyrophosphate [27] (Fig. 6.10). In this case the group was removed by irradiation in 0.05 M-KOH solution. 

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