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有机化学 ›› 2008, Vol. 28 ›› Issue (04): 672-679. 上一篇    下一篇

研究论文

烃基硅铜酸盐与2-芳基-2-环烯酮1,4-加成反应的立体选择性及2-取代- 3-硅基环烷酮的合成

唐子龙*,a,b，易平贵a，刘汉文a   

  1. (a湖南科技大学化学化工学院 分子构效关系湖南省高校重点实验室 湘潭 411201)
    (b Laboratory of Organic Synthesis Chemistry, Catholique University of Louvain, B-1348 Louvain-la-Neuve, Belgium)
  • 收稿日期:2007-07-23 修回日期:2007-09-18 发布日期:2008-04-17
  • 通讯作者: 唐子龙

Stereoseletivity of 1,4-Addition of Dialkylphenylsilyl Cuprates to 2-Aryl-2-cycloenones and Synthesis of 2-Substituted-3-silylcy-cloalkanones

TANG Zi-Long*,a,b,YI Ping-Guia,LIU Han-Wena   

  1. (a Key Laboratory of QSAR/QSPR of Hunan Provincial University, School of Chemis-try and Chemical Engineering,
    Hunan University of Science and Technology, Xiangtan 411201)
    (b Laboratory of Organic Synthesis Chemistry, Catholique University of Louvain, B-1348 Louvain-la-Neuve, Belgium)
  • Received:2007-07-23 Revised:2007-09-18 Published:2008-04-17
  • Contact: TANG Zi-Long

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2

研究了烷基苯基硅铜酸盐与2-环烯酮的1,4-加成反应的立体选择性, 并合成了一系列新的2-取代-3-硅基环烷酮. 结果表明, 在0 ℃下用饱和NH4Cl溶液处理, 烷基苯基硅铜酸盐与2-芳基-2-环烯酮的1,4-加成反应的立体选择性不同程度地受芳基和环的大小影响, 得到顺、反两种产物; 并首次发现室温下用甲醇处理反应时, 其立体选择性不受或者很少受环大小、芳基的性质以及与硅原子相连的取代基的影响, 只得到反式产物. 芳基溴甲烷与由烷基苯基硅铜酸盐与2-环烯酮1,4-加成所得的烯醇盐反应时, 只得到反式产物. 合成产物的结构用IR, 1H NMR, 13C NMR, MS和HRMS等进行了表征.

关键词: 烷基苯基硅铜酸盐, 合成, 2-环烯酮, 2-取代-3-硅基环烷酮, 1,4-加成反应, 立体选择性

The stereoselectivity of 1,4-addition of dialkylphenylsilyl cuprates to 2-cycloenones was investigated and meantime a series of new 2-substituted-3-silylcycloalkanones were synthesized. It was found that the stereoselectivity of the 1,4-addition of dialkylphenylsilyl cuprates to 2-aryl-2-cycloenones depended on the nature of aryl group and ring size by quenching the reactions with saturated NH4Cl solution at 0 ℃. However, it was first found that the addition gave very high trans selectivity independent of the aryl group, ring size and substituents on the silicon atom by quenching the reactions with methanol at room temperature. It was also observed that arylmethyl bromides reacted with enolates resulting from 1,4-addition of dimethylphenylsilyl cuprate to 2-cycloenones giving exclusively trans isomers. All products were characterized by IR, 1H NMR, 13C NMR, MS and HRMS spectra.

Key words: 2-cycloenone, synthesis, dialkylphenylsilyl cuprate, 1,4-addition, 2-substituted-3-silylcycloalkanone, stereoselectivity