Phosphoranylation de polyols: Voie d'accès aux phosphates d'intérêt biologique. I. Cas du myo-inositol

Abstract

Requ le 26 janvier 1988 BRIGITTE DUTHU, DOURAID HOUALLA et ROBERT WOLF. Can. J. Chem. 66, 2965Chem. 66, (1988. Nous dicrivons une rnCthode originale de phosphorylation du rnyo-inositol non protCgC, qui fournit plusieurs myo-inositol phosphates A la fois. Le schema reactionnel cornporte une phosphoranylation totale ou partielle du cyclitol, I'aide de l'arninobicyclophosphane 8, suivie d'une oxydation des bicyclophosphoranes liaison P-H obtenus et d'une hydrolyse acide des phosphates neutres qui en rCsultent. Dans le cas de la tris-phosphoranylation nous avons identifie, parmi les fractions sCparCes par HPLC, le myo-inositol-l,2(cycl) phosphate 22, le myo-inositol-1 phosphate 23 et le myo-inositol-2 phosphate 24.BRIGITTE DUTHU, DOURAID HOUALLA, and ROBERT WOLF. Can. J. Chem. 66, 2965Chem. 66, (1988. An original method for the phosphorylation of an unprotected myo-inositol is described, which yields several rnyo-inositol phosphates at the same time. The reaction proceeds via a partial or complete phosphoranylation of the cyclitol by means of the aminobicyclophosphane 8, followed by oxidation of the resulting bicyclophosphoranes bearing a P-H bond and acid hydrolysis of the neutral phosphates thus formed. In the case of the tris-phosphoranylation we identified, among the HPLC fractions, the myo-inositol-l,2-(cyc1)phosphate 22, the myo-inositol-1-phosphate 23, and the myo-inositol-2-phosphate 24.

Recent advances in the chemistry and biochemistry of inositol phosphates of biological interest

“…Enantiomerically pure D-myO-inOSitOl 1,3,4,5tetrakisphosphate has been synthesized by resolution of the diol (1 5 I), prepared from racemic 1,2 : 4,5-biscyclohexylidenemyo-inositol (53) by selective 3-benzoylation, benzylation at (86). Chemoselective tin-mediated allylation of the equatorial hydroxyl group of ( 85) to (154), followed by benzylation of the 2-hydroxyl group to (155) and deallylation gave the tetrol (1 38) which was phosphitylated using N,Ndiethyl dibenzylphosphoramidite, the product oxidized with Bu'OOH to (139) and hydrogenolysed to give D-inositol-1,3,4,5-tetraki~phosphate. '~~…”

Structure cristalline et moléculaire d'un composé tricyclique contenant le cycle à dix chaînons dioxo diaza diphosphécine

“…De mCme, les doublets a 6 = 82,l pprn et 6 = 84,8 pprn dans celui de 3 sont respectivement attribuables aux noyaux de carbone C(53) et C(52). Les deplacements chimiques des noyaux de carbone des cycles a cinq chainons sont en accord avec les valeurs relevees pour les mCmes noyaux de carbone dans le monomkre 1 (6).…”

Bis(dimethylamino)phosphorodiamidate: A Reagent for the Regioselective Cyclophosphorylation of cis-Diols Enabling One-Step Access to High-Value Target Cyclophosphates

“…Because of its structural complexity, only a few (but unsuccessful) efforts have been made to explore the chemical-phosphorylation of unprotected inositol in one step. , Bruzik et al . and Vishwakarma and co-workers have demonstrated the enzymatic synthesis of various of O -alkyl inositol phosphates via inositol-1,2-cyclic phosphate (IcP) by using the PI-PLC enzyme.…”