SYNTHESIS OF NEW ANHYDRO AND BRANCHED-CHAIN CYCLITOLS

Starting from D-glucose and D-(-)-quinic acid (5) (1S,5R,6S)-5-azido-6 -benzyloxycyclohex- 2-en-l-ol (3), and the structurally related alpha, beta-unsaturated alcohols 7 and 8, respectively, were prepared. They h ave been transformed, by treatment with 3-chloroperoxybenzoic acid, in to ,5S,6R)-3-azido-2-benzyloxy-5,6-epoxycyclohex-1-ol (4) and the two diastereoisomeric 4,5-isopropylidenedioxycyclohexane-l-ols 9 and 10. T hermal Claisen rearrangement of the allylic alkcohols 3, 7 and 8 resul ted in the functionalized branched-chain cyclohexenyl acetamides 12, 1 3 and 14, respectively. The prepared new cyclitols are useful starting materials for further derivatization to obtain novel enzyme-inhibitor s, including phosphorylated cyclitols with ''second-messenger'' proper ties. (C) 1997 Elsevier Science Ltd.