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有机化学
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有机化学 ›› 2005, Vol. 25 ›› Issue (04): 424-426. 上一篇    下一篇

研究论文

钌1,2-萘醌-1-肟配合物对aldol C—C成键反应的催化作用

孙克，张宝砚，刘晓霞*   

  1. (东北大学化学系 沈阳 110004)
  • 收稿日期:2004-02-27 修回日期:2004-11-10 发布日期:2005-03-30
  • 通讯作者: 刘晓霞

Catalysis of Ruthenium 1,2-Naphthoquinone-1-oxime Complexes towards Aldol C—C Bond Formation Reactions

SUN Ke,ZHANG Bao-Yan,LIU Xiao-Xia*   

  1. (Department of Chemistry, Northeastern University, Shenyang 110004)
  • Received:2004-02-27 Revised:2004-11-10 Published:2005-03-30
  • Contact: LIU Xiao-Xia

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在钌1,2-萘醌-1-肟(1-nqo)配合物cis,cis-[Ru(1-nqo)2(CO)(NCMe)] (1)或trans,trans-[Ru(1-nqo)2(PBu3)2] (2)的作用下, 氰基乙酸乙酯与取代苯甲醛发生aldol C—C成键反应. 根据GC-MS检测及HPLC分离结果, 对二苯甲醛的二个醛基可分别或同时与氰基乙酸乙酯发生aldol反应. 1H NMR表征结果证明, 二种产物的双键构型均为反式. 其它取代苯甲醛的反应均给出单一反式aldol产物, 这表明该催化反应具有立体选择性. 配合物1的催化活性稍差, 产率不超过60%, 而配合物2的催化活性要高于1, 最高产率达99%.

关键词: C—C成键反应, 钌, 1,2-萘醌-1-肟

Aldol C—C bond formation reactions of ethyl cyanoacetate with benzaldehydes were catalyzed by ruthenium 1,2-naphthoquinone-1-oxime (1-nqo) complex, cis,cis-[Ru(1-nqo)2(CO)(NCMe)] (1) or trans,trans- [Ru(1-nqo)2(PBu3)2] (PBu3＝tributylphosphine) (2). The reactions were monitored by GC and the products were characterized by GC-MS and 1H NMR spectra. Except the reaction of p-formylbenzaldehyde that gave both single and double adducts, a single aldol product was detected in the catalytic reactions. 1H NMR measurement of the purified products indicated that the stereochemistry of the products is E, showing the anti-selectivity of the catalytic reaction. The yield of 2 catalyzed reactions is higher than that of 1.

Key words: 1,2-naphthoquinone-1-oxime, C—C bond formation reaction, ruthenium