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有机化学
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有机化学 ›› 2006, Vol. 26 ›› Issue (05): 727-729. 上一篇    下一篇

研究简报

(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环[2.2.1]-2-庚烯的合成及结构表征

裴文*，孙莉，王海滨，王永江，邵越水   

  1. (浙江工业大学化学工程与材料学院 杭州 310014)
  • 收稿日期:2005-01-27 修回日期:2005-11-28 发布日期:2006-04-28
  • 通讯作者: 裴文

Synthesis and Characterization of (5R,6R)-6-Phenyl-5-(phenylsulfonylacetyl)bicyclo[2.2.1]hept-2-ene

PEI Wen*,SUN Li,WANG Hai-Bin,WANG Yong-Jiang,SHAO Yue-Shui   

  1. (College of Chemical Engineering and Materials, Zhejiang University of Technology, Hangzhou 310014)
  • Received:2005-01-27 Revised:2005-11-28 Published:2006-04-28
  • Contact: PEI Wen

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报道了一种制备4-苯基-1-苯磺酰基-3-丁烯-2-酮的新合成方法. 4-苯基-3-丁烯-2-酮与溴化试剂Ph3P＋CH2CH2- COOHBr 作用, 得到1-溴-4-苯基-3-丁烯-2-酮, 不经分离直接与苯亚磺酸钠发生亲核取代反应, 得到4-苯基-1-苯磺酰基-3-丁烯-2-酮. 将此反应产物作为亲双烯体与环戊二烯在手性钛金属催化剂催化下进行不对称Diels-Alder反应, 得到了＞99% ee 的环加成产物(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环[2.2.1]-2-庚烯. 用X衍射法对产物的晶体结构进行了测定, 讨论了反应机理, 通过元素分析, NMR, MS对产物的结构进行了表征.

关键词: 机理, 不对称催化, 合成, Diels-Alder反应, 苯磺酰基不饱和酮, 晶体结构

A new method for preparation of 4-phenyl-1-phenylsulfonyl-3-butene-2-one was developed. 1-Bromo-4-phenyl-3-butene-2-one was obtained by the bromination of 4-phenyl-3-butene-2-one with , then reacted with sodium benzene sulfinate directly to give 4-phenyl- 1-phenylsulfonyl-3-butene-2-one in good yield. (5R,6R)-6-Phenyl-5-(phenylsulfonylacetyl)bicyclo[2.2.1]- hept-2-ene with＞99% ee was obtained by the asymmetric Diels-Alder reaction of 4-phenyl-1-phenylsulfonyl-3-butene-2-one with cyclopentadiene catalyzed by chiral titanium reagent. The asymmetric reaction mechanism was discussed and the adduct was characterized by X-ray, IR, MS and NMR spectra.

Key words: Diels-Alder reaction, synthesis, crystal structure, phenylsulfonyl unsaturated ketone, mechanism, asymmetric catalysis