有机化学 ›› 2019, Vol. 39 ›› Issue (7): 1976-1982.DOI: 10.6023/cjoc201812020 上一篇    下一篇

研究论文

8-异戊烯基黄酮类天然产物的微波促进Claisen重排合成

李蔚a, 宿亮a, 汪秋安a, 李高阳b, 单杨b   

  1. a 湖南大学化学化工学院 长沙 410082;
    b 湖南省农业科学院农产品加工研究所 长沙 410125
  • 收稿日期:2018-12-11 修回日期:2019-03-01 出版日期:2019-07-25 发布日期:2019-03-29
  • 通讯作者: 汪秋安 E-mail:wangqa@hnu.edu.cn
  • 基金资助:

    果蔬加工与质量安全湖南省重点实验室(No.2108TP1030)和湖南省自然科学基金(No.2018JJ2034)资助项目.

Synthesis of 8-Prenylflavonoids Natural Products by Microwave Promoted Claisen Rearrangement

Li Weia, Shu Lianga, Wang Qiuana, Li Gaoyangb, Shan Yangb   

  1. a College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082;
    b Institution of Agricultural Product Processing, Hunan Academy of Agricultural Science, Changsha 410125
  • Received:2018-12-11 Revised:2019-03-01 Online:2019-07-25 Published:2019-03-29
  • Contact: 10.6023/cjoc201812020 E-mail:wangqa@hnu.edu.cn
  • Supported by:

    Project supported by the Key Laboratory of Hunan Province for Fruit and Vegetable Processing and Quality Safety (No. 2108TP1030) and the Hunan Provincial Natural Science Foundation of China (No. 2018JJ2034).

8-异戊烯基黄酮是一类具有显著生物活性的天然产物.以2,4,6-三羟基苯乙酮和3,4-二羟基苯甲醛为原料,用氯甲基甲醚保护羟基,经羟醛缩合、碘催化环合、过氧丙酮(DMDO)氧化、O-异戊烯基化、微波促进的Claisen重排、脱甲氧甲基保护基、O-甲基化和异戊烯基侧链环合等反应步骤,完成了8-异戊烯基槲皮素-3-甲醚(1)、8-异戊烯基槲皮素-3,7,3',4'-四甲醚(2)和Artochamin C(3)这3种8-异戊烯基黄酮类天然产物的合成.并对由微波促进的由5-O-异戊烯基黄酮类化合物合成8-C-异戊烯基黄酮类化合物的Claisen重排反应的关键步骤进行了探讨.所有合成的化合物经1H NMR、13C NMR和MS等结构确证.

关键词: 8-异戊烯基槲皮素-3-甲醚, 8-异戊烯基槲皮素-3,7,3',4'-四甲醚, Artochamin C, 微波促进Claisen重排

8-Prenylflavonoids are a class natural products with significant biological activities. The total synthesis of three prenylflavonoid natural products, 8-prenylquercetin-3-methylether (1), 8-prenylquerccetin-3,7,3',4'-tetramethyl ether (2) and Artochamin C (3), was achieved through methoxymethyl protection, aldol condensation, iodine catalytic cyclization, dimethyl sulfoxide (DMSO) oxidation, O-prenylation, microwave promoted Claisen rearrangement, deprotection, O-methylation and prenyl group side chain cyclization, staring from commercially available 2,4,6-trihydroxyacetophenone and 3,4-dihydroxy benzaldehyde. The key step of microwave promoted Claisen rearrangement formed 8-C-prenylflavonoids from 5-O- prenylflavonoids was investigated. All the synthesized compounds were confirmed by 1H NMR、13C NMR and MS techniques.

Key words: 8-prenylquercetin-3-methyl ether, 8-prenylquercetin-3,7,3',4'-tetramethyl ether, artochamin C, microwave promoted Claisen rearrangement