Synthesis of cyclohexitol with a stereospecific method

A new method for preparation of a sugar molecule that has cyclohexitol construction was realized. Dihydro cyclohexene bis-dimethanol (1) was prepared by reduction of maleic anhydrite. Acetylation (Ac2O/pyridine) of dihydro cyclohexene bis-dimethanol (1) and bromonation of double bond gave (4,5-dibromocyclohexane-1,2-diyl)bis(methylene) diacetate (3) with high yield. By elimination of 2 mol HBr cyclohexa-2,4-diene-1,2-diylbis(methylene) diacetate (4) was synthesized. Cyclohexa-2,4-diene-1,2-diylbis(methylene) diacetate was subjected to 2+4 cycloaddition reaction 5 with singled oxygen and by homolitic cleavage of resultant oxgen-oxgen bonds (tiyoüre/MeOH) and ((1R,2S,5S)-2,5-dihydroxycyclohex-3-ene-1,2-diyl)bis(methylene) diacetate (6) was synthesized quantitatively.Acetilation of ((1R,2S,5S)-2,5-dihydroxycyclohex-3-ene-1,2-diyl)bis(methylene) diacetate (6) (Ac2O/pirydine) gave ((1R,2S,5S)-5-acetoxy-2-hydroxycyclohex-3-ene-1,2-diyl)bis(methylene) diacetate (7) with high yield. Methylenic double bond of compound 7 was epoxidized by MCPBA to give ((1S,2S,3R,5S,6S)-5-acetoxy-2-hydroxy-7-oxa-bicyclo[4.1.0]heptane-2,3-diyl)bis(methylene) diacetate (8) and by opening and acetilaton of epoxide in acidic medium (1S,4S,5R)-4,5-bis(acetoxymethyl)-4-hydroxycyclohexane-1,2,3-triyl triacetate (9) was sythesized. By hydrolization (NH3(g)/MeOH) of compound 9 in basic medium (1S,4S,6R)-1,6-bis(hydroxymethyl)cyclohexane-1,2,3,4-tetraol (10) synthesized quantitatively.