Simple and Efficient Routes to Optically Active chiro- and allo-Inositol Derivatives from myo-Inositol

Abstract

Efficient routes for the gram scale syntheses of optically active chiro- and allo-inositol derivatives from readily available 1,2:4,5-di-O-isopropylidene-myo-inositol (1) are described. Both d and l forms of these isomeric inositols could be synthesized from enantiomers of 1. One-pot methodology for the simultaneous synthesis of both chiro and allo has also been developed. The possible selectivity for the cleavage of trans-ketal in presence of the cis is an added advantage for the syntheses of a variety of protected deri­vatives for phosphoinositol syntheses. These routes provide synthetically flexible 1,2:4,5-di-O-isopropylidene-chiro-inositol and 1,6:3,4-di-O-isopropylidene-allo-inositol which are difficult to achieve otherwise.

cyclitols - inositols - regioselectivity - carbohydrates - ­inhibitors

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To a solution of diol 1D (260 mg, 1 mmol) and pyridine (2 mL) in CH₂Cl₂ (10 mL) was added Tf₂O (255µL, 1.5 mmol) dropwise at -20 °C. The reaction mixture was stirred overnight at r.t. The solvents were evaporated and the residue was dissolved in EtOAc, washed successively with H₂O, cold diluted HCl, sat. aq NaHCO₃ and brine, dried (Na₂SO₄) and evaporated. The crude mixture of 3D and 4D thus obtained was dissolved in DMA (7 mL) and reacted with KOAc (500 mg, 5 mmol) at 70-80 °C for 5 h. DMA was evaporated and usual work-up of the residue followed by column chromatography yielded 5L (124 mg, 41%) and 8D (186 mg, 54%).