Studies on biosynthesis of lignans in woody plants.

木本植物木脂素生物合成的研究。

基本信息

批准号：
05660177
负责人：
OZAWA Shuji
金额：
$ 1.34万
依托单位：
HOKKAIDO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1995
项目状态：
已结题

项目摘要

Lignans and neolignans are a widely distributed, structurally diverse phytochemical class in gymnosperms and angiosperms, with exhibiting various biological activities.As a part of our studies to elucidating biosynthetic pathways of lignans in woody plants, we investigated the formation of lignans in Magnolia kobus DC var. borealis Sarg. and Abies sachalinensis Masters.Based on structural considaratin and possible transformations, we obtained various lignans in recemic ((]SY.+-.]))-form by total synthesis. They were ((]SY.+-.]))-pinoresinol, ((]SY.+-.]))-monomethylpinoresinal, ((]SY.+-.]))-eudesmin, ((]SY.+-.]))-syringaresinol, ((]SY.+-.]))-monomethylsyringaresinol, ((]SY.+-.]))-yangambin, ((]SY.+-.]))-kobusin, ((]SY.+-.]))-fargesin and ((]SY.+-.]))-piperitol. In addition, [9,9-^2H_2, OC^2H_3] coniferyl alcohol and [3-O^<14>CH_3] monomethylpinoresinol were synthesized.In vivo labelling experiments of M.kobus DC var. borealis, it was established that deuterated coniferyl alcohol had been incorporated into pinoresinol, but not fargesin and kobusin. These results suggested that formation of pinoresinol can occur via coupling of two intact coniferyl alcohol moieties. Next, we examined O-methylation reaction of ((]SY.+-.]))-pinoresinol by incubation with cell-free extracts from M.kobus DC var. borealis. It was shown that M.kobus DC var. borealis cell-free extracts catalysed the O-methylation of pinoresinol, suggesting the conversion of pinoresinol into monomethylpinoresinol and eudesmin in Magnolia.In the investigation of lignans of Abies sachalinensis various lignans were isolated. it revealed that lignans of Abies sachalinensis were characterized by a preferential occurerence of lactol-type lignans, which mainly distributed in the sap-and heartwood. it was suggested that abiesol A (phenylpropane trimer) was derived from the coupling of lariciresinol (tetrahydrofuran type lignan) and coniferyl alcohlol. (monolignol).

木脂素和新木脂素是裸子植物和被子植物中分布广泛、结构多样的一类植物化学物质，具有多种生物活性。作为阐明木本植物木脂素生物合成途径研究的一部分，我们研究了木兰中木脂素的形成。。北极星萨尔格。基于结构考虑和可能的转化，我们通过全合成获得了各种rememic((]SY.+-.]))-形式的木脂素。它们是((]SY.+-.]))-松脂醇、((]SY.+-.]))-单甲基松脂醛、((]SY.+-.]))-eudesmin、((]SY.+ -.]))-丁香树脂醇、((]SY.+-.]))-单甲基丁香树脂醇、((]SY.+-.]))-yangambin、 ((]SY.+-.]))-科布辛、((]SY.+-.]))-箭黄素和((]SY.+-.]))-胡椒醇。此外还合成了[9,9-^2H_2,OC^2H_3]松柏醇和[3-O^14CH_3]单甲基松脂醇。北极线虫中，已确定氘代松柏醇已掺入松脂醇中，但没有掺入法吉辛和科布辛。这些结果表明松脂醇的形成可以通过两个完整的松柏醇部分的偶联而发生。接下来，我们通过与 M.kobus DC var. 的无细胞提取物一起孵育来检查 ((]SY.+-.]))-松脂醇的 O-甲基化反应。北极星。结果表明，M.kobus DC 变种。北极香杉无细胞提取物催化松脂醇的O-甲基化，表明木兰中松脂醇转化为单甲基松脂醇和桉树素。在对高山冷杉木脂素的研究中，分离出了多种木脂素。结果表明，冷杉木脂素的特点是优先存在乳醇型木脂素，主要分布在树液和心材中。有人提出，abiesol A（苯丙烷三聚体）是由落叶松树脂醇（四氢呋喃型木酚素）和松柏醇偶联而成。（单木质醇）。