The thio-Mitsunobu reaction of D-glucitol, D-mannitol, galactitol and 1-seleno-D-xylitol

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. Rearrangeme nt (acetyl group migration) to form 3-O-acetyl-1,4-anhydro-6-thio-D-glucito l 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-ma nnitol, 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. (C) 2000 Elsevier Science Ltd. All rights reserved.