Studies on biosynthesis of lignans in woody plants.

木脂素和新木脂素是裸子植物和被子植物中广泛存在的一类结构多样的植物化学物质，具有多种生物活性。北方藻和冷杉（Abies sachalinensis Masters）中的木脂素类化合物，并对其结构和可能的转化进行了分析，在外消旋（（]SY.+-.]））-全合成的形式。他们是（（]SY.+-.]））-松醇，（（]SY.+-.]））-单甲基半夏醛，（（]SY.+-.]））-桉结蛋白，（（）SY.+-.]））-姜黄树脂酚，（（]SY.+-.]））-单甲基双松脂醇，（（[SY.+.]））- yangambin，（（]SY.+-.]））- kobusin，（（]SY.+-.]））- fargesin和（（]SY.+-.]））-胡椒醇。此外，还合成了[9，9-^2H_2，OC^2H_3]松柏醇和[3-<14>O^CH_3]单甲基松柏醇。在Borealis中，确定氘代松柏醇已掺入到松醇中，但未掺入到法格辛和kobusin中。这些结果表明，通过两个完整的松柏醇部分的偶联可以形成松醇。接下来，我们检查了（（]SY.+-.]））-的O-甲基化反应。通过与来自M.kobus DC var.北极光结果表明，牦牛DC变种。结果表明，在木兰科植物中，华北冷杉无细胞提取物催化了松醇的O-甲基化反应，表明松醇转化为单甲基松醇和桉叶结蛋白。结果表明，高山冷杉木脂素以乳醇型木脂素为主，主要分布在心材和边材中。结果表明，冷杉醇A（苯基丙烷三聚体）是由落叶松树脂酚（四氢呋喃型木脂素）与松柏醇偶联而得。（monolithyl）。

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).