Sharma M, Bernacki R J, Hillman M J, Korytnyk W
Grace Cancer Drug Center, Roswell Park Memorial Institute, Buffalo, New York 14263.
Carbohydr Res. 1993 Feb 24;240:85-93. doi: 10.1016/0008-6215(93)84174-5.
Treatment of benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-alpha-D-allopyranoside with diethylaminosulfur trifluoride or of the 3-O-mesyl derivative with tetrabutylammonium fluoride gave the 2,3-unsaturated compound instead of the expected 3-deoxy-3-fluoro derivative. The latter was obtained when benzyl 2-acetamido-4,6-di-O-benzyl-2-deoxy-3-O-mesyl-alpha-D-allopyran oside was treated with potassium fluoride. Methyl 2-azido-4,6-O-benzylidene-2-deoxy-alpha-D-altropyranoside was converted into the 2-acetamido- and 2-phthalimido-3-O-mesyl derivatives; when treated with fluoride nucleophile, these gave only the 2,3-aziridine derivative. However, treatment of the 2-azido-2-deoxy derivative with diethylaminosulfur trifluoride gave methyl 2-azido-2,3-dideoxy-3-fluoro-alpha-D-mannopyranoside which, after reduction, deprotection, and acetylation, gave the acetylated derivative of methyl 2-acetamido-2,3-dideoxy-3-fluoro-alpha-D-mannopyranoside in excellent yield. These acetylated 3-fluoro derivatives exhibited inhibition of cell growth of murine L1210 leukemia cells in culture at micromolar concentrations.
用二乙氨基三氟化硫处理2-乙酰氨基-4,6-O-亚苄基-2-脱氧-α-D-阿洛吡喃糖苷苄酯，或用四丁基氟化铵处理3-O-甲磺酰基衍生物，得到的是2,3-不饱和化合物，而不是预期的3-脱氧-3-氟衍生物。当用氟化钾处理2-乙酰氨基-4,6-二-O-苄基-2-脱氧-3-O-甲磺酰基-α-D-阿洛吡喃糖苷苄酯时，可得到后者。2-叠氮基-4,6-O-亚苄基-2-脱氧-α-D-阿卓吡喃糖苷甲酯被转化为2-乙酰氨基和2-邻苯二甲酰亚氨基-3-O-甲磺酰基衍生物；当用氟亲核试剂处理时，这些衍生物只得到2,3-氮丙啶衍生物。然而，用二乙氨基三氟化硫处理2-叠氮基-2-脱氧衍生物，得到2-叠氮基-2,3-二脱氧-3-氟-α-D-甘露吡喃糖苷甲酯，该化合物经还原、脱保护和乙酰化后，以优异的产率得到2-乙酰氨基-2,3-二脱氧-3-氟-α-D-甘露吡喃糖苷甲酯的乙酰化衍生物。这些乙酰化的3-氟衍生物在微摩尔浓度下对培养的小鼠L1210白血病细胞的生长具有抑制作用。
