| Beckmann裂解反应在天然产物Fumagillin和Ovalicin前体及衍生物全合成中的应用 |
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| 引用本文： | 林成刚,祝曙英,全旭,邱银华,史海健.Beckmann裂解反应在天然产物Fumagillin和Ovalicin前体及衍生物全合成中的应用[J].合成化学,2010,18(6). |
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| 作者姓名： | 林成刚 祝曙英 全旭 邱银华 史海健 |
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| 作者单位： | 南京工业大学化学化工学院; |
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| 基金项目： | 江苏省高校自然科学基金 |
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| 摘 要： | 以Hajos酮为原料,经环氧化、酸催化开环、烷基化(或酰基化)仲羟基、一步立体选择性氢化/缩酮保护等反应,方便地在双环适当的位置引入烷氧基,再应用PCl5/2,6-二甲基吡啶/CH2Cl2进行Beckmann裂解反应,将五员环开环生成相应的烯-腈化合物,高收率地合成了Fumagillin和Ovalicin前体及衍生物3-1-烷氧基-5,5-(1,2-亚乙二氧基-5-甲烯基)环己基丙腈(7a~7d)和2-甲氧基-3-丙腈-4-甲烯基环己酮(8a),并构建其重要的手性环状骨架。化合物的的结构经NMR,IR和MS确证,其中8a为未见文献报道的新化合物。
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| 关 键 词： | Hajos酮 Beckmann裂解反应 一步氢化/缩酮保护 立体选择性合成 全合成 |
Beckmann Fragmentation Applying in the Synthesis of Chiral Precursor and Derivative of Fumagillin and Ovalicin |
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| LIN Cheng-gang,ZHU Shu-ying,QUAN Xu,QIU Yin-hua,Shi Hai-jian.Beckmann Fragmentation Applying in the Synthesis of Chiral Precursor and Derivative of Fumagillin and Ovalicin[J].Chinese Journal of Synthetic Chemistry,2010,18(6). |
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| Authors: | LIN Cheng-gang ZHU Shu-ying QUAN Xu QIU Yin-hua Shi Hai-jian |
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| Institution: | LIN Cheng-gang,ZHU Shu-ying,QUAN Xu,QIU Yin-hua,Shi Hai-jian(College of Chemistry and Chemical Engineering,Nanjing University of Technology,Nanjing 210009,China) |
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| Abstract: | A series of important precursor and skeleton of Fumagillin and Ovalicin,3-1-alkoxy-5,5-(1,2-ethylenedioxy)-5-methylene)hexamethylene-propionitrile(7a~7d) and new chiral(2R,3S)-2-methoxyl-3-propanenitrile-4-methylenecyclohexone(8a),were synthesized by epoxidation of Hajos-Parish ketone,acid-catalyzed hydrolysis of epoxide,alkylation(or acetylation) of the secondary alcohol,one-pot stereoselective hydrogenation/acetalization and Beckmann fragmentation.The structures were characterized by NMR,IR and MS. |
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| Keywords: | Hajos ketone Beckmann fragmentation one-pot hydrogenation/acetalization stereoselective synthesis total synthesis |
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