Synlett 2004(3): 493-496  
DOI: 10.1055/s-2004-815443
LETTER
© Georg Thieme Verlag Stuttgart · New York

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

Kana M. Sureshan, Yutaka Watanabe*
Department of Applied Chemistry, Faculty of Engineering, Ehime University, Matsuyama, 790-0607 Japan
Fax: +81(89)9279944; e-Mail: wyutaka@dpc.ehime-u.ac.jp;
Further Information

Publication History

Received 5 December 2003
Publication Date:
06 February 2004 (online)

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.

20

This compound did not melt on heating but charred in the temperature range 110-130 °C.

22

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%).