The thio-Mitsunobu reaction of d-glucitol, d-mannitol, galactitol and 1-seleno-d-xylitol Original Research Article

Unprotected d-glucitol is transformed into 5-O-acetyl-1,4-anhydro-6-thio-d-glucitol (3) in one step by use of the thio-Mitsunobu reaction. Rearrangement (acetyl group migration) to form 3-O-acetyl-1,4-anhydro-6-thio-d-glucitol occurs during column chromatography of 3 on silica gel. 2,5-Di-O-acetyl-1,6-dithio-d-mannitol and 1,6-di-S-acetyl-2,5-anhydro-1,6-dithio-d-glucitol (characterized as the corresponding p-nitrobenzoates) are formed from d-mannitol, whereas galactitol yields a mass of unidentified products. 1-Seleno-d-xylitol, produced by reduction of d-xylose with hydrogen selenide, does not undergo a Mitsunobu reaction.