中文摘要
本项目选取具有新颖结构骨架的虎皮楠生物碱苷 Longeracinphyllin C 为研究对象,采取多种手段,开展对生物碱合成关键步骤D-A加成反应机制研究,为寻找新的 D-A酶 提供基础和科学依据。.在生物合成方面,我们采用了计算模拟以及无细胞体系培养。与吴云东院士合作,采用计算化学方法,开展生物碱合成关键步骤D-A加成反应研究,结果显示反应过程应是协同进行而且需要酶催化。.在Longeracinphyllin C 的合成方面,我们先后采用化学改造和全合成方法合成关键中间体带有环戊二烯结构单元的calyciphylline AA类生物碱。与杨震、王智刚教授合作,设计了生物碱双烯体的合成方法,目前已完成构建AB, 6-7-5-5四环模型化合物的合成,全合成正在进行并已接近尾声。.此外,我们还开展了国产虎皮楠科植物中新颖结构生物碱成分的研究。发表论文15篇。已有8个化合物被国际权威刊物Nat.Prod. Rep.列为““热点化合物”丰富并发展了天然产物的研究方法。
英文摘要
The project selects Longeracinphyllin C, a novel type Alkaloids with an iridoid glucoside moiety isolated from Daphniphyllum Longeracemosum, as biosynthesis and total synthesis subject. We use various methods to study the rational mechanism of the key step, which provide theoretical base for new Diels-Alderase..As for biosynthesis, computational modeling and cell-free system were employed. We demonstrated that the Diels-Alder reaction, as a key biosynthetic step in the formation of Longeracinphyllin C, should be synengistic and corresponding enzyme should also be involved. As for total synthesis of Longeracinphyllin C, chemical modification and total synthesis of key intermidiate Calyciphylline A type alkaloids were employed. Till now, two model compounds with AB and 6-7-7-5 four-ring system were synthesized by our cooperator, Prof. Wang and Yang. With consideration of the previous results,we redesigned synthestic route of Dapgniyunnine D, and now the total synthesis is on the way..Furthermore, alkaloids from Daphniphyllaceae in china were also studied. Part of results were pubilshed in 15 papers.Among them, 8 compounds were collected as "Hot Off Press" in well-known magzine Natural Products Reports.
结题摘要
本项目选取具有新颖结构骨架的虎皮楠生物碱苷 Longeracinphyllin C 为研究对象,采取多种手段,开展对生物碱合成关键步骤D-A加成反应机制研究,为寻找新的 D-A酶 提供基础和科学依据。在生物合成方面,我们采用了计算模拟以及无细胞体系培养。与吴云东院士合作,采用计算化学方法,开展生物碱合成关键步骤D-A加成反应研究,结果显示反应过程应是协同进行而且需要酶催化。在Longeracinphyllin C 的合成方面,我们先后采用化学改造和全合成方法合成关键中间体带有环戊二烯结构单元的calyciphylline AA类生物碱。与杨震、王智刚教授合作,设计了生物碱双烯体的合成方法,目前已完成构建AB, 6-7-5-5四环模型化合物的合成,全合成正在进行并已接近尾声。此外,我们还开展了国产虎皮楠科植物中新颖结构生物碱成分的研究。发表论文15篇。已有8个化合物被国际权威刊物Nat.Prod. Rep.列为““热点化合物”丰富并发展了天然产物的研究方法。
