Franck R W, Kaila N
Department of Chemistry, Hunter College/CUNY, NY 10021.
Carbohydr Res. 1993 Feb 1;239:71-83. doi: 10.1016/0008-6215(93)84204-j.
Arylbis(arylthio)sulfonium salts have been used to activate glycals towards nucleophilic addition to form principally 2-deoxy-beta-glycosides. This method was applied to the synthesis of the 2-(methylphenylthio)-2'-phenylthio derivative (22) of methyl O-(4-O-benzyl-2,6-dideoxy-beta-D-arabino- hexopyranosyl)-(1-->3)-3,4-di-O-benzyl-2,6-dideoxy-2,6-beta-D-arabino- hexopyranoside, the C'D' ring analog of an aureolic acid disaccharide. The condensation of 1,5-anhydro-2,6-dideoxy-D-arabino-hex-1-enitol with methanol in the presence of the phenylbis(phenylthio)sulfonium salt resulted in formation of the first beta-glycoside linkage. The methyl 6-deoxyglucoside obtained was deprotected at HO-3 to give the 2-thiophenyl-substituted 2,6-dideoxy-beta-glucoside. This was coupled with 1,5-anhydro-3,4-di-O-benzyl-2-deoxy-D-arabino-hex-1-enitol in the presence of 4-methylphenyl[bis(4-methylphenyl)thio]sulfonium salt to give the (1-->3)-linked disaccharide 22. Finally, desulfurization of 22 using WII Raney nickel generated the required 2,2'-dideoxydisaccharide.
芳基双（芳硫基）锍盐已被用于活化缩水甘油醛以进行亲核加成反应，主要生成2-脱氧-β-糖苷。该方法被应用于合成甲基O-（4-O-苄基-2,6-二脱氧-β-D-阿拉伯-己吡喃糖基）-（1→3）-3,4-二-O-苄基-2,6-二脱氧-2,6-β-D-阿拉伯-己吡喃糖苷的2-（甲基苯硫基）-2'-苯硫基衍生物（22），它是金霉素酸二糖的C'D'环类似物。在苯基双（苯硫基）锍盐存在下，1,5-脱水-2,6-二脱氧-D-阿拉伯-己-1-烯醇与甲醇缩合，形成了第一个β-糖苷键。得到的甲基6-脱氧葡萄糖苷在HO-3处脱保护，得到2-硫代苯基取代的2,6-二脱氧-β-葡萄糖苷。在4-甲基苯基[双（4-甲基苯基）硫基]锍盐存在下，将其与1,5-脱水-3,4-二-O-苄基-2-脱氧-D-阿拉伯-己-1-烯醇偶联，得到（1→3）连接的二糖22。最后，使用WII雷尼镍对22进行脱硫反应，生成所需的2,2'-二脱氧二糖。
