The preparation of phosphorylated intermediates for the synthesis of racemic and chiral myo-inositol 1,4,5-trisphosphate and its phosphorothioate analogues

Article abstract of DOI:10.1016/0008-6215(92)85046-3

Reaction of racemic 1,2,4-tri-O-benzyl-myo-inositol 3- with bis(2,2,2-trichloroethyl) phosphorochloridate gave a mixture of the 3,5- and 3,6-bisphosphate derivatives which were difficult to separate and could not be phosphorylated further.The bisphosphates were synthesised by the phosphorylation of the 5- and 6-O-(cis-prop-1-enyl) derivatives of racemic 1,2,4-tri-O-benzyl-myo-inositol and subsequent acidic hydrolysis. 1D-2,3,6-Tri-O-benzyl-1,4-di-O-(cis-prop-1-enyl)-myo-inositol was converted into crystalline 1D-2,3,6-tri-O-benzyl-myo-inositol 1,4-bis(dibenzyl phosphate), and thence into the crystalline 1,4,5-tris(dibenzyl phosphate) which was also obtained, using dibenzyloxy(diisopropylamino)phosphine, from 1D-2,3,6-tri-O-benzyl-myo-inositol.The latter compound was converted, using bis(2-cyanoethoxy)(diisopropylamino)phosphine, into the crystalline 1,4,5-tris which was also obtained from the 4,5-bis.Both the tris and the tris(dibenzyl phosphate) are intermediates suitable for the synthesis of 1,4,5-IP₃.