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有机化学
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有机化学 ›› 2010, Vol. 30 ›› Issue (05): 726-730. 上一篇    下一篇

研究论文

9,10-二氢苯并[h]香豆素类化合物的双羟化反应研究及酯化产物的合成

王洁1，夏鹏*,1，王洋*,1,2   

  1. (1复旦大学药学院药物化学教研室 上海 201203)
    (2中国科学院上海药物研究所新药研究国家重点实验室 上海 201203)
  • 收稿日期:2010-02-26 修回日期:2010-03-29 发布日期:2010-04-07
  • 通讯作者: 王洋 E-mail:wangyang@shmu.edu.cn
  • 基金资助:

    国家自然科学基金

Dihydroxylation of 9,10-Dihydrobenzo[h]coumarins and Synthesis of Their Ester Derivatives

Wang Jie1 Xia Peng*,1 Wang Yang*,1,2   

  1. (1 Department of Medicinal Chemistry, School of Pharmacy, Fudan University, Shanghai 201203)
    (2 State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203)
  • Received:2010-02-26 Revised:2010-03-29 Published:2010-04-07
  • Contact: Yang WANG E-mail:wangyang@shmu.edu.cn

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报道了在9,10-二氢苯并[h]香豆素类化合物1a, 1b的不对称双羟化反应中, 除了得到正常的cis-7,8-双羟化产物2a, 2b外, 还以中等收率(52%和45%)得到了过度氧化产物7-羰基-8-羟基化合物3a, 3b, 并讨论了氧化剂用量及反应温度对产物分布的影响. 双羟化产物2a, 2b的ee值通过其樟脑酯化产物4a, 4b的1H NMR图谱所示的非对映异构体比例进行了初步推测. 过度氧化产物3b及其樟脑酯化产物5b的结构经X射线单晶衍射分析确证.

关键词: 9,10-二氢苯并[h]香豆素, 双羟化反应, 过度氧化, 樟脑酯化产物

The asymmetric dihydroxylation of 9,10-dihydrobenzo[h]coumarins (1a, 1b) provided not only enantiomerically enriched cis-7,8-diols (2a, 2b) but also 7-keto-8-hydroxy compounds 3a, 3b which were obtained in moderate yields (52% and 45%, respectively) by the overoxidation of the corresponding diols. The influence of the amount of oxidant and the reaction temperature on the distribution of products were discussed and the ee values of the diols 2a, 2b were deduced approximately from the diasteromeric ratios of their corresponding camphanoyl esters (4a, 4b) by 1H NMR spectra. The structures of overoxidation product 3b and its camphanoyl ester 5b were determined by X-ray diffraction analysis.

Key words: 9,10-dihydrobenzo[h]coumarin, dihydroxylation, overoxidation, camphanoyl ester