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，我们研究了木兰木脂素的形成。北极熊(Borealis Sarg.)根据木脂素的结构构型和可能的转化，我们通过全合成得到了(()sy.+-.))形式的各种木脂素。它们是(()sy.+-.])-松脂醇，(()sy.+-.]))-单甲基松脂素，(()sy.+-.]))-丁香素，(()sy.+-.]))-丁香酚，(()sy.+-.]))-单甲基丁香酚，(()sy.+-.]))-洋甘斌，((]sy.+-.]))-Kobusin，(()SY.+-.]))-精氨酸和(()SY.+-.])-匹珀醇。此外，还合成了[9，9-^2H_2，OC^2H_3]松柏醇和[3-O^&lt；14&gt；CH_3]单甲基松脂醇。北方松脂醇中含有氢化松柏醇，而不是松脂素和葛根素。这些结果表明，松脂醇的形成可以通过两个完整的针叶醇部分的偶联来实现。接下来，我们研究了(()sy.+-.])-松脂醇的O-甲基化反应。北极星。结果表明，黑曲霉属变种。北方冷杉无细胞提取物催化松脂醇O-甲基化，提示松脂醇在木兰素中转化为单甲基松脂醇和桉树素。在对冷杉木脂素的研究中，分离到了各种木脂素。结果表明，冷杉木脂素以乳糖醇型木脂素为主，主要分布在树干和心材中。结果表明，松香醇A(苯丙烷三聚体)是落叶松脂醇(四氢呋喃类木脂素)与松柏醇偶联的产物。(单甘醇)。

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).