Entymatic transfer of the caffeic acid to the glucosyl moiety of caffeic sugar esters

咖啡酸向咖啡糖酯的葡萄糖基部分的酶促转移

• 批准号: 11660159
• 负责人: OTA Michikazu
• 金额: $ 2.43万
• 依托单位: Iwate University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11660159/
• 关键词: Paulownia tomentosa Steud.; Caffeoyltransferase; 2-oxoisoacteoside; 3,4-di-O-allylcaffeic acid; 1-(3,4-diallyloxyphenyl)-2-hydroxy-1-ethanone; Deprotection; acetyl group; allyl group; 2-oxo-2-(3,4-di-hydroxyphenyl)-ethyl 3-O-α-L-rhamnpyranosyl-6-O

The preparation of caffeoyl : CoA ligase and caffeoyltransferase from the leaves of Paulownia tomentosa Steud. is still in progress in this stage of research, but as another aspect of this study, the following results were obtained ; 2-oxoisoacteoside (2-oxo-2-(3,4-dihydroxyphenyl)-ethyl 3-O-α-L-rhamnopyranosyl-6-O- caffeoyl-β-D-glucopyranoside) was chemically synthesized from glucose in the 21 reaction steps (main 13 steps) with total yield of 7.4 %. l,2-O-acetyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl) -6-O-acetyl-D-glucopyranose (3) was prepared from 1,2 : 5,6-di-O-isopropylidene-3-O-(2,3,4-tri-O-acetyl-L-rhamnopyranosyl)-D- glucofuranose in the 5 reaction steps with yield of 47 %. 3,4-di-O-allylcaffeic acid(2") was prepared from protocatechuic acid in the 2 reaction steps with yield of 67 %. 1,2-O-acetyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnosyl) -4-O-(3,4-O-allyl caffeoyl)-6-O-acetyl-D-glucopyranose (4) was prepared from compounds 3 and 2" with yield of 98 % in the presence of DCC, DMAP, and DMAP-HCl. 2-oxo-2-(3',4'-diallyloxyphenyl)-ethyl 2-O-acetyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-4-O-(3,4-O-diallyl caffeoyl)-6-O-acetyl-D-glucopyranoside was prepared from compound 4 and 1-(3,4-diallyloxyphenyl)-2-hydroxy-1-ethanone (2"') in the 3 reaction steps with yield of 53 %. Compound 2" was prepared from 2-chloroacetyl catechol in the 3 reaction steps with yield of 44 %. Compound 5 was deprotected with yield of 76 %, giving 2-oxoisoacteoside. Deprotection of acetyl group resulted in migration of caffeoyl group to C-6-OH of glucose moiety in compound 5.

毛泡桐叶中咖啡酰：CoA连接酶和咖啡酰转移酶的制备。本研究的另一个方面是以葡萄糖为原料，经21步反应（主要13步）合成了2-氧代异丙酮酸糖苷（2-氧代-2-（3，4-二羟基苯基）-乙基3-O-α-L-吡喃鼠李糖基-6-O-咖啡酰基-β-D-吡喃葡萄糖苷），总收率为7.4%。以1，2：5，6-二-O-异亚丙基-3-O-（2，3，4-三-O-乙酰基-α-L-吡喃鼠李糖基）-D-呋喃葡萄糖为原料，经5步反应制得1，2-O-乙酰基-3-O-（2，3，4-三-O-乙酰基-α-L-吡喃鼠李糖基）-6-O-乙酰基-D-吡喃葡萄糖（3），产率为47%。以原儿茶酸为原料，经2步反应制得3，4-二-O-烯丙基咖啡酸（2”），收率67%。化合物3和2”在DCC、DMAP和DMAP-HCl存在下合成了1，2-O-乙酰基-3-O-（2，3，4-三-O-乙酰基-α-L-鼠李糖基）-4-O-（3，4-O-烯丙基咖啡酰基）-6-O-乙酰基-D-吡喃葡萄糖（4），产率98%。以化合物4和1-（3，4-二烯丙氧基苯基）-2-羟基-1-乙酮（2“'）为原料，经3步反应制得2-氧代-2-（3'，4 '-二烯丙氧基苯基）-乙基2-O-乙酰基-3-O-（2，3，4-三-O-乙酰基-α-L-吡喃鼠李糖基）-4-O-（3，4-O-二烯丙基咖啡酰基）-6-O-乙酰基-D-吡喃葡萄糖苷，收率53%。化合物2”由2-氯乙酰基邻苯二酚经3步反应制得，产率为44%。化合物5脱保护，产率76%，得到2-氧代异毛蕊花糖苷。乙酰基的脱保护导致化合物5中咖啡酰基迁移到葡萄糖部分的C-6-OH。