新型海参硫酸软骨素葡萄糖受体及葡萄糖醛酸受体的高效合成

Efficient Synthesis of Novel Glucose and Glucuronic Acid Acceptors for Sea Cucumber Chondroitin Sulfate Preparation

以D-葡萄糖为起始原料,经9步反应合成了2-O-苄基-3-O-烯丙基-1-O-对甲氧基苯基-α-D-葡萄糖(9);将9的6-位伯羟基经叔丁基二苯基硅烷基(TBDPS)保护,首次合成了正交保护的新型葡萄糖受体2-O-苄基-3-O-烯丙基-6-O-叔丁基二苯基硅烷基-1-O-对甲氧基苯基-α-D-葡萄糖(Ⅱ),总收率28.2%;将9的6-位伯羟基氧化糖醛酸化后,再经甲酯化,以25.0%的总收率首次合成了新型葡萄糖醛酸受体2-O-苄基-3-O-烯丙基-1-O-对甲氧基苯基-α-D-葡萄糖醛酸甲酯(Ⅲ),化合物结构经1H NMR,13C NMR,IR和HR-MS(ESI)表征。

p-Methoxyphenyl 2-O-benzyl-3-O-allyl-a-D-glucopyranoside （9） was synthesized from D- glucose by nine step reactions. The primary hydroxyl of 9 was protected by tert-butyldiphenysilyl（TB- DPS） to afford the novel orthogonal protected glucose acceptor p-methoxyphenyl 2-O-benzyl-3-O-allyl- 6-O-tert-butyldiphenysilyl-a-D-glucopyranoside （Ⅱ） for the first time, in total yield of 28.2%. Oxida- tion of the primary hydroxyl of 9, followed by esterification with iodine methane, provided the new glucu- ronic acid acceptor methyl （p-methoxyphenyl 2-O-benzyl-3-O-allyl-a-D-glucopyranoside） uronate（Ⅲ）, in total yield of 25.0%. The structures were characterized by 1H NMR, 13C NMR and HR-MS（ESI）.