Fakha Ghada, Sinou Denis
Laboratoire de Synthèse Asymétrique, CPE Lyon, Université Claude Bernard Lyon 1, France.
Molecules. 2005 Aug 31;10(8):859-70. doi: 10.3390/10080859.
Epoxidation and cis-hydroxylation of C-phenyl-delta(2,3)-glycopyranosides have been carried out with a view to developing C-aryl glycoside synthesis. Epoxidation of (2,3- and (6-O-tert-butyldimethylsilyl-2,3-dideoxy-D-erythro-hex-2-enopyranosyl)benzenedideoxy-D-erythro-hex-2-enopyranosyl)benzene gave predominantly the allo-adducts whatever the configuration at the anomeric center. Epoxidation of (4,6-di-O-tert-butyl-dimethylsilyl-2,3-dideoxy-D-erythro-hex-2-enopyranosyl)benzene gave the manno- and allo-adducts in a 89:11 and 40:60 ratios for the alpha- and beta-anomers, respectively. Hydroxylation of alpha-C-phenyl-(2,3)-glycopyranosides using OsO4 afforded the manno-adduct only, whatever the substituents at positions 4 and 6, whereas hydroxylation of (2,3-dideoxy-beta-D-erythro-hex-2-enopyranosyl)benzene and (4,6-di-O-tert-butyldimethylsilyl-2,3-dideoxy- beta-D-erythro-hex-2-enopyranosyl)benzene gave the manno- and allo-adducts in 25:75 and 80:20 ratios, respectively.
为了开发C-芳基糖苷合成方法，已经进行了C-苯基-δ(2,3)-吡喃葡萄糖苷的环氧化和顺式羟基化反应。(2,3-和(6-O-叔丁基二甲基甲硅烷基-2,3-二脱氧-D-赤藓糖己-2-烯吡喃糖基)苯二脱氧-D-赤藓糖己-2-烯吡喃糖基)苯的环氧化反应，无论异头中心的构型如何，主要生成别-加合物。(4,6-二-O-叔丁基二甲基甲硅烷基-2,3-二脱氧-D-赤藓糖己-2-烯吡喃糖基)苯的环氧化反应，对于α-和β-异头物，分别以89:11和40:60的比例生成甘露-和别-加合物。使用OsO4对α-C-苯基-(2,3)-吡喃葡萄糖苷进行羟基化反应，无论4位和6位的取代基如何，仅生成甘露-加合物，而(2,3-二脱氧-β-D-赤藓糖己-2-烯吡喃糖基)苯和(4,6-二-O-叔丁基二甲基甲硅烷基-2,3-二脱氧-β-D-赤藓糖己-2-烯吡喃糖基)苯的羟基化反应，分别以25:75和80:20的比例生成甘露-和别-加合物。
