Phosphate tribenzyl

Tribenzyl phosphate and tetrabenzyl pyrophosphate are hyperalkylating agents and produce quaternary amine salts,... 

Problem 13.58 Inorganic acids such as HjSO , H,PO, and HOCI (hypochlorous acid) form esters. Write structural formulas for (a) dimethyl sulfate, (b) tribenzyl phosphate, (e) diphenyl hydrogen phosphate, (d) /-butyl nitrite, (e) lauryl hydrogen sulfate (lauryl alcohol is n-CuH jCH OH), (/) sodium lauryl sulfate. ... 

When 6 -deoxy-5 -iodo-2, 3 -0-isopropylideneuridine (203) is treated with silver dibenzyl phosphate or with silver tribenzyl pyrophosphate, the protected 5 -nucleotide (205, R = benzyl or dibenzyl phosphoric) was obtained after removal of the protecting groups, this gave uridine 5 -phos-phate (206, R = H) and uridine 5 -pyrophosphate (R = POsHa). It is possible that, in the formation of (205) from (203), anhydronucleoside (204) was an intermediate which underwent attack by the phosphoric... 

To achieve total synthesis of inositol phosphates and related derivatives, multiple phosphorylation of polyol derivatives is the most crucial step. Use of dianilinophosphoric chloride 8 was the only method of choice for this purpose. However, its reactivity is not satisfactory for perphosphorylation of inositols and furthermore spontaneous deprotection of several dianilinophosphoric esters in the same molecules is quite difficult, while phosphorylation of D-2,3,6-tribenzyl-myo-inositol 9 with the chloride 8 giving 11 in 60% yield was accomplished after exploring proper reaction conditions in the first total synthesis of Ins(l,4,5)P3 (Scheme 2-1).However, the phosphorylation product 12 was not formed at all from 10, a positional isomer of 9 under similar conditions. In 1987, it was reported that the reaction of tetrabenzyl pyrophosphate (TBPP, 13) with alkoxides generated in situ by the action of a strong base such as NaH.l c KH, - or butyllithium b on inositols smoothly gave the desired polyphosphorylated products in good yields. Examples are shown in Scheme 2-1. 

Inositol L-form 1,2,3,5-Tetra-O-angeloyl, 1-28 -Inositol L-form 1,2,4,5-Tetra-O-angeloyl, 1-28 -Inositol l,2 3,4-Di-0-cyclohexylidene, 5-benzoyl, 1-30 wyo-Inositol 1,4-Diphosphate, 1-32 wyo-Inositol 1-0-p-D-Glucopyranoside, nona-Me, 1-32 wyo-Inositol hexakis(phosphate), 1-32 wyo-Inositol monoorthoformate, 1-32 wyo-Inositol 1,2,3,4,5-Pentaphosphate, 1-32 wyo-Inositol 1,2,3,4,6-Pentaphosphate, 1-32 myo-Inositol 1,2,3,5,6-Pentaphosphate, 1-32 myo-Inositol 1,2,4,5,6-Pentaphosphate, 1-32 myo-Inositol 1,3,4,5,6-Pentaphosphate, 1-32 myo-Inositol 2,3,4,5,6-Pentaphosphate, 1-32 myo-Inositol 1-Phosphate, ( ), 1-32 myo-Inositol 4-Phosphate, ( ), 1-32 myo-Inositol 1-Phosphate, 1-32 myo-Inositol 2-Phosphate, 1-32 myo-Inositol 3-Phosphate, 1-32 myo-Inositol 4-Phosphate, 1-32 myo-Inositol 5-Phosphate, 1-32 myo-Inositol 6-Phosphate, 1-32 myo-Inositol 3,4,5,6-Tetra-Ac, 1-32 myo-Inositol 2,3,5,6-Tetrabenzyl, 1-32 myo-Inositol 1,3,4,5-Tetraphosphate, 1-32 myo-Inositol 1,3,5,6-Tetraphosphate, 1-32 myo-Inositol 1,4,5,6-Tetraphosphate, 1-32 myo-Inositol 3,4,5,6-Tetraphosphate, 1-32 myo-Inositol 2,4,6-TVibenzyl, 1,3,5-0-methylidyne, 1-32 myo-Inositol 2,3,5-Tribenzyl, 1-32 myo-Inositol 1,2,3-Triphosphate, 1-32 myo-Inositol 1,3,4-Triphosphate, 1-32 myo-Inositol 1,4,5-Triphosphate, 1-32 myo-Inositol 1,4,6-Triphosphate, 1-32 myo-Inositol 2,4,5-Triphosphate, 1-32 myo -Inositol-1,2,6-triphosphate, 1-32 fl//o-Inositol, 1-27 i -Inositol, 1-28 /-Inositol, 1-28 cw-Inositol, 1-29 ep/-Inositol, 1-30 mwco-Inositol, 1-31... 

The Miller group was the first to report catalytic asymmetric phosphorylation of alcohols, in 2001 [81]. They reported that D-myo-inositol-l-phosphate 82 could be prepared with high levels of enantiomeric purity by the ASD of 2,4,6-tribenzyl-myo-inositol (81) using diphenyl(chloro)phosphate and triethylamine in toluene at 0°C catalyzed by 2mol% of pentapeptide 79, which contains an N-terminal TT-methyl histidine residue as the nucleophile (Scheme 41.29). 

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