發(fā)布時間：2018-04-16 15:15

  本文選題：羥醛反應 + 仿生合成��； 參考：《蘭州大學》2017年博士論文

【摘要】：本論文敘述了近年來光誘導的烯烴[2+2]環(huán)加成反應,并針對異海綿烷二萜kravanhins A-C與石松生物堿annotinolide B開展了合成研究。該論文共包括三章:第一章光誘導的烯烴[2+2]環(huán)加成反應(綜述)簡要綜述了近20年內(nèi)烯烴通過紫外光直接激發(fā)或光敏化作用發(fā)生[2+2]光環(huán)加成反應的進展。本綜述按照受激發(fā)的烯烴的共軛類型,對非共軛烯烴、芳基共軛的烯烴、α,β-不飽和酮以及α,β-不飽和羧酸衍生物分別進行討論。第二章異海綿烷二萜Kravanhins A-C的全合成簡要介紹了海綿烷二萜的分離與合成研究。我們以結(jié)構(gòu)新穎的異海綿烷四環(huán)二萜kravanhins A-C作為合成目標。第一代合成以13步6.2%的總產(chǎn)率完成了(-)-kravanhin B的首次不對稱全合成。關(guān)鍵步驟是用分子內(nèi)aldol環(huán)化反應構(gòu)筑了trans-anti-cis三環(huán)骨架并用酸催化的脫水反應串聯(lián)烯烴異構(gòu)化反應構(gòu)筑了丁烯內(nèi)酯環(huán)。第二代合成是以仿生的策略對(-)-kravanhins A和C進行全合成。我們提出了半日花烷二萜轉(zhuǎn)化成異海綿烷二萜的生源假說,并以此對(-)-kravanhins A和C進行了反合成分析。整個合成先通過匯聚的策略合成了呋喃型的半日花烷二萜衍生物,再通過1O2參與的光氧化反應得到γ-羥基丁烯內(nèi)酯型半日花烷二萜衍生物。然后,用γ-羥基丁烯內(nèi)酯通過關(guān)鍵的aldol環(huán)化串聯(lián)內(nèi)酯化反應合成了異海綿烷二萜(-)-kravanhin C,最后通過區(qū)域選擇性與立體選擇性的還原反應得到了(-)-kravanhin A。這部分工作對探索自然界中萜類的生源轉(zhuǎn)化具有參考意義。第三章石松生物堿Annotinolide B的合成研究簡要介紹了石松生物堿lycopodine的分離以及一部分代表性的合成研究。我們以結(jié)構(gòu)新穎的五環(huán)石松生物堿annotinolide B作為合成目標。關(guān)鍵反應是通過aldol縮合反應構(gòu)筑A環(huán),并通過光誘導的烯烴[2+2]環(huán)加成反應合成四元環(huán)與內(nèi)酯環(huán)。目前,我們已經(jīng)用aldol縮合構(gòu)筑了A環(huán),實現(xiàn)了ABC三環(huán)骨架的構(gòu)筑。這部分工作正在進行中。
[Abstract]:In this paper, the photoinduced cycloaddition reaction of olefin [22] was described, and the synthesis of isosomonane diterpene kravanhins A-C with pine alkaloid annotinolide B was studied.The thesis consists of three chapters: chapter 1: light induced [22] cycloaddition reaction of olefin (review). The progress of [22] cycloaddition reaction of olefins by direct excitation or Guang Min reaction by ultraviolet light in the last 20 years is briefly reviewed.In this review, the conjugation of unconjugated olefin, aryl conjugated olefin, 偽, 尾 -unsaturated ketone and 偽, 尾 -unsaturated carboxylic acid derivatives are discussed according to the conjugation types of activated olefin.In chapter 2, the isolation and synthesis of Kravanhins A-C from isomonitane diterpene were introduced briefly.Kravanhins A-C, a novel tetracyclic diterpene, was used as the synthesis target.The first asymmetric total synthesis of the first generation was completed with a total yield of 6.2% in 13 steps.The key step is to construct the trans-anti-cis tricyclic skeleton by intramolecular aldol cyclization and to construct the butenolactone ring with the dehydration reaction catalyzed by acid and the series isomerization of olefins.The second generation of synthesis is a bionic strategy for the total synthesis of Con-Kravanhins A and C.We put forward the biogeneration hypothesis of the conversion of diterpene from hemihelianane to isomorphine diterpene, and based on this hypothesis, we have carried out a reverse synthesis analysis of the two diterpenes, I. e., Cran-kravanhins A and C.Firstly, furan type diterpene derivatives were synthesized by convergent strategy, and then 緯 -hydroxybutenolactone diterpene derivatives were synthesized by photooxidation of 1O2.Then, the isosomonane diterpene triterpene -Kramvanhin C was synthesized by using 緯 -hydroxybutene lactone through the key aldol cyclization series esterification reaction. Finally, the regioselectivity and stereoselectivity reduction reaction resulted in the synthesis of the iso-cavernine diterpene and the stereoselectivity reduction reaction.This part of the work has reference significance for exploring the biotransformation of terpenoids in nature.In the third chapter, the synthesis of Annotinolide B alkaloids of Pinus lanceolata was introduced. The separation of lycopodine and the synthesis of some representative alkaloids were briefly introduced.Annotinolide B, a novel alkaloid of Pinus pentacyclic, was used as the synthesis target.The key reaction is to construct A ring by aldol condensation reaction and to synthesize four member ring and lactone ring by photoinduced [22] cycloaddition reaction of olefins.At present, we have constructed A-ring by aldol condensation, and have realized the construction of ABC three-ring skeleton.This part of the work is under way.
【學位授予單位】：蘭州大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O621.3

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相關(guān)期刊論文 前2條

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2 譚昌恒,朱大元;石松生物堿研究進展[J];中國天然藥物;2003年01期

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本文編號：1759480