Dibenzyl phosphorofluoridate

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. ... 

Synthesis of Phosphoric Acids and their Derivatives.-New approaches to the preparation of dialkyl phosphorofluoridates include the treatment of a vinyl phosphate, e.g.,(l), or an irninophosphace, e.g.,(2), with triethylamine tris(hydrogen fluoride) when the alkyl group consists of a suitably protected nucleoside, the reaction between mono(crimethylsilyl) phosphite in pyridine and sulphuryl chloride fluoride at -30° has been successfully explored. Dibenzyl phosphorofluorldate, hitherto unreported, has been obtained from tecrabenzyl diphosphate and caesium fluoride, and also from the reaction between dibenzyl hydrogen phosphate and 2-fluoro-N-methylpyridinlum tosylate. ... 

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