Grzeszczyk B, Zamojski A
Instytut Chemii Organicznej PAN w Warszawie.
Postepy Hig Med Dosw. 1996;50(5):483-91.
Five monophosphates of L-glycero-D-manno-heptose having the PO(OH)2 residue at O-2,3, 4, 6, and 7 have been synthesized starting from suitably protected benzyl D-mannopyranoside derivatives. The synthesis involved chain elongation by the reaction of D-mannoside 6-aldehyde with alkoxymethylmagnesium chloride resulting in the desired L-glycero-D-manno-heptopyranoside as the main product. The blocking groups pattern enabled selective deprotection of the hydroxyl groups at C-2, 3, 4, and 7. These substrates were phosphitylated with 2-dimethylamino-5,6-benzo-1,3,2-dioxaphosphepan and oxidized in situ to phosphates. The resulting products were hydrogenolytically deprotected and converted to di(cyclohexylammonium) salts which were characterized by 13C-NMR spectra.
以适当保护的苄基-D-甘露吡喃糖苷衍生物为起始原料，合成了5种L-甘油-D-甘露庚糖的单磷酸酯，其PO(OH)₂残基分别位于O-2、3、4、6和7位。合成过程包括D-甘露糖苷6-醛与烷氧基甲基氯化镁反应进行链延长，从而得到所需的L-甘油-D-甘露庚吡喃糖作为主要产物。保护基模式使得能够选择性地脱除C-2、3、4和7位羟基的保护。这些底物用2-二甲基氨基-5,6-苯并-1,3,2-二氧磷杂环戊烷进行磷酰化，并原位氧化成磷酸盐。所得产物经氢解脱保护，转化为二环己基铵盐，并通过¹³C-NMR光谱进行表征。
