胆汁酸的24-β-D-吡喃半乳糖苷的化学合成：人尿中一种新型的胆汁酸共轭物。

Chemical synthesis of 24-beta-D-galactopyranosides of bile acids: a new type of bile acid conjugates in human urine.

作者信息

Kakiyama Genta, Sadakiyo Shinji, Iida Takashi, Mushiake Kumiko, Goto Takaaki, Mano Nariyasu, Goto Junichi, Nambara Toshio

机构信息

Department of Chemistry, College of Humanities and Sciences, Nihon University, Sakurajousui, Setagaya, Tokyo 156-8550, Japan.

出版信息

Chem Phys Lipids. 2005 Apr;134(2):141-50. doi: 10.1016/j.chemphyslip.2005.01.002.

DOI:10.1016/j.chemphyslip.2005.01.002

PMID:15784232

Abstract

A method is reported for the preparation of the C-24 carboxyl-linked beta-D-galactopyranosides of lithocholic, deoxycholic, chenodeoxycholic, ursodeoxycholic, and cholic acids, two of which were recently identified as a novel type of the metabolites of bile acids excreted in human urine. Direct esterification (galactosidation) of the unprotected bile acids with 2,3,4,6-tetra-O-benzyl-D-galactopyranose in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent and subsequent hydrogenolysis of the resulting benzyloxy-protected bile acid 24-beta-D-galactopyranosides over 10% palladium on charcoal under atmospheric pressure afforded the title compounds. The structures of the bile acid acyl galactosides were confirmed by measuring several (1)H-(1)H and (1)H-(13)C shift correlated 2D NMR.

摘要

报道了一种制备石胆酸、脱氧胆酸、鹅去氧胆酸、熊去氧胆酸和胆酸的C-24羧基连接的β-D-吡喃半乳糖苷的方法，其中两种最近被鉴定为人类尿液中排泄的胆汁酸的一种新型代谢产物。在2-氯-1,3,5-三硝基苯作为偶联剂的存在下，将未保护的胆汁酸与2,3,4,6-四-O-苄基-D-吡喃半乳糖直接酯化（半乳糖苷化），随后在大气压下，将所得苄氧基保护的胆汁酸24-β-D-吡喃半乳糖苷在10%钯-炭上进行氢解，得到标题化合物。通过测量几个1H-1H和1H-13C位移相关的二维核磁共振谱确定了胆汁酸酰基半乳糖苷的结构。