Catalytic Lewis acid phosphorylation with pyrophosphates

Recent advances in synthetic and medicinal chemistry of phosphotyrosine and phosphonate-based phosphotyrosine analogues

“…16 Fenton et al reported the Lewis acid catalyzed phosphorylation with pyrophosphates (Scheme 1, path H). 76 Titanium(IV) tert-butoxide was found to be the most effective catalyst for the reaction of Boc-Tyr-OMe with tetrabenzylpyrophosphate (Scheme 4). Other pyrophosphates with methyl, ethyl, allyl, and o-nitrobenzyl protecting groups are synthetically available and might serve as phosphorylating agents.…”

Alternative synthetic tools to phospho-specific antibodies for phosphoproteome analysis: progress and prospects

“…Sculimbrene et al [50] have recently reported an alternative catalytic procedure for the phosphorylation of primary and secondary alcohols, utilizing titanium-based Lewis acids and pyrophosphates [P(V) reagents]. Use of tetrabenzylpyrophosphate (TBPP, 1.2 eq.)…”

“…This procedure incorporates the use of a base (in this case N i Pr 2 Et) to provide efficient catalytic turnover by acting as an acid scavenger and allows the use of a P(V) phosphorylating agent, thus avoiding the formation of elimination Scheme 7 Pyridine N-oxides in phosphotriester bond formation (adapted from Efimov et al 1985) [51] products associated to the use of P(III) reagents followed by subsequent oxidation (Entry 6, Table 1). Sculimbrene et al [50] again, however, describe the phosphorylation of tertiary alcohols using these conditions as being inefficient. This procedure provides marginally improved yields in comparison to the previously described use of tetrazole-based catalysts in conjunction with isocyanates (Table 1).…”

A convenient method for phosphorylation using triallyl phosphite

“…11,12 Several methods have been reported for the synthesis of allyl-protected phosphates, 10 namely the use of diallyl chlorophosphate 1, 12,13 phosphoramidite 2 2,7-9,14,15 and, more recently, the catalytic Lewis acid phosphorylation with pyrophosphates such as compound 3. 16 However, the combination of phosphite and iodine, a cheap, easy-to-handle method which does not require prior synthesis of the reagent, has never been reported for access to allyl phosphates whereas it is an established method for the introduction of methyl, ethyl or benzyl protected phosphates. 17 Moreover, triallyl phosphite is commercially available and quite inexpensive, or it can be easily prepared from phosphorus trichloride.…”