软体动物系列糖基神经酰胺α-D-甘露糖基-(1→3)-β-D-甘露糖基-(1→4)-β-D-葡萄糖基-(1→1)-神经酰胺和α-D-甘露糖基-(1→3)-[β-D-木糖基-(1→2)]-β-D-甘露糖基-(1→4)-β-D-葡萄糖基-(1→1)-神经酰胺的全合成。

Total synthesis of the mollu-series glycosyl ceramides alpha-D-Manp-(1----3)-beta-D-Manp-(1----4)-beta-D-Glcp-(1----1)-Cer and alpha-D-Manp-(1----3)-[beta-D-Xylp-(1----2)]-beta-D-Manp-(1----4)-beta- D-Glcp-(1----1)-Cer.

作者信息

Mori M, Ito Y, Ogawa T

机构信息

RIKEN (The Institute of Physical and Chemical Research), Saitama, Japan.

出版信息

Carbohydr Res. 1990 Jan 15;195(2):199-224. doi: 10.1016/0008-6215(90)84167-s.

DOI:10.1016/0008-6215(90)84167-s

PMID:2331702

Abstract

The mollu-series glycosphingolipids, O-alpha-D-mannopyranosyl-(1----3)-O-beta-D-mannopyranosyl-(1----4)-O-bet a-D-glucopyranosyl-(1----1)-2-N-tetracosanoyl-(4E)-sphingeni ne and O-alpha-D-mannopyranosyl-(1----3)-O-[beta-D-xylopyranosyl-(1----2])-O- beta-D-mannopyranosyl-(1----4)-O-beta-D-glucopyranosyl-(1----1)-2-N- tetracosanoyl-(4E)-sphingenine, were synthesized for the first time by using 2,3,4-tri-O-acetyl-D-xylopyranosyl trichloroacetimidate, methyl 2,3,4,6-tetra-O-acetyl-1-thio-alpha-D-mannopyranoside, benzyl O-(4,6-di-O-benzyl-beta-D-mannopyranosyl)-(1----4)-2,3,6-tri-O-benzyl-be ta-D- glucopyranoside 9, and (2S,3R,4E)-2-azido-3-O-(tert-butyldiphenylsilyl)-4-octade cene-1,3-diol 6 as the key intermediates. The hexa-O-benzyl disaccharide 9 was prepared by coupling two monosaccharide synthons, namely, 2,3-di-O-allyl-4,6-di-O-benzyl-alpha-D-mannopyranosyl bromide and benzyl 2,3,6-tri-O-benzyl-beta-D-glucopyranoside. It was demonstrated that azide 6 was highly efficient as a synthon for the ceramide part in the coupling with both glycotriaosyl and glycotetraosyl donors, particularly in the presence of trimethylsilyl triflate.

摘要

首次使用2,3,4-三-O-乙酰基-D-吡喃木糖基三氯乙酰亚胺酯、甲基2,3,4,6-四-O-乙酰基-1-硫代-α-D-吡喃甘露糖苷、苄基O-(4,6-二-O-苄基-β-D-吡喃甘露糖基)-(1→4)-2,3,6-三-O-苄基-β-D-吡喃葡萄糖苷9和(2S,3R,4E)-2-叠氮基-3-O-(叔丁基二苯基硅基)-4-十八碳烯-1,3-二醇6作为关键中间体，合成了软脂酰系列糖鞘脂，即O-α-D-吡喃甘露糖基-(1→3)-O-β-D-吡喃甘露糖基-(1→4)-O-β-D-吡喃葡萄糖基-(1→1)-2-N-二十四烷酰基-(4E)-鞘氨醇和O-α-D-吡喃甘露糖基-(1→3)-O-[β-D-吡喃木糖基-(1→2)]-O-β-D-吡喃甘露糖基-(1→4)-O-β-D-吡喃葡萄糖基-(1→1)-2-N-二十四烷酰基-(4E)-鞘氨醇。六-O-苄基二糖9是通过偶联两个单糖合成子制备的，即2,3-二-O-烯丙基-4,6-二-O-苄基-α-D-吡喃甘露糖基溴和苄基2,3,6-三-O-苄基-β-D-吡喃葡萄糖苷。结果表明，叠氮化物6作为合成子用于与糖三糖基和糖四糖基供体偶联时，在合成神经酰胺部分方面效率很高，特别是在三氟甲磺酸三甲基硅酯存在的情况下。