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有机化学
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有机化学 ›› 2006, Vol. 26 ›› Issue (05): 653-659. 上一篇    下一篇

研究论文

De Mayo光环加成和桥(螺)环倍半萜基本碳架的构建

王进军*,1，纪建业2，森章3   

  1. (1烟台大学应用化学系 烟台 264005)
    (2通化师范学院化学系 通化 134002)
    (3九州大学机能物质研究所 日本)
  • 收稿日期:2005-08-03 修回日期:2005-11-16 发布日期:2006-04-28
  • 通讯作者: 王进军

De Mayo Photocycloaddition and Construction of Basic Framework for Spiro- and Bridged-sesquiterpenes

WANG Jin-Jun*,1,JI Jian-Ye2,MORI Akira3   

  1. (1 Department of Applied Chemistry, Yantai University, Yantai 264005)
    (2 Department of Chemistry, Tonghua Teachers College, Tonghua 134002)
    (3 Institute of Advanced Material Study, Kyushu University, Japan)
  • Received:2005-08-03 Revised:2005-11-16 Published:2006-04-28
  • Contact: WANG Jin-Jun

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通过烃单萜3-甲基-6-异丙亚甲基环己烯(1)和2,6-二氧代戊酸甲酯(2)的de Mayo反应, 得到[2＋2]环加成产物、开环产物和游离基复合产物3～10. 经retro-aldol重排, 环加成产物3开环生成取代环己烯4, 在酸和碱性介质中对开环产物进行再环合, 经分子内Claisen缩合反应形成螺环和桥环化合物11～14. 讨论了可能的反应机理, 对所得新化合物的结构经IR, 1H NMR, 13C NMR及元素分析予以确定.

关键词: Claisen缩合反应, 螺环化合物, 桥环环合物, 光环加成

The photocyclo-adducts, the opening products and radical recombination products 3～10 were obtained by de Mayo reaction of 3-isopropylidene-6-methylcyclohexene with methyl 2,4-dioxopentanoate. The photocyclo-adduct 3 was subjected to retro-aldol rearrangement to yield the substituted-cyclohexene 4. In acid or basic condition the recyclization of the opening product was carried out, and spirocyclic and bridged compounds 11～14 were obtained by intramolecular Claisen condensation. The reaction mechanisms were discussed and the structures of all compounds were assigned based on the data derived from IR, 1H NMR 13C CMR and elemental analysis.

Key words: spirocyclic compound, bridged compound, Claisen condensation, photocycloaddition