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有机化学 ›› 2009, Vol. 29 ›› Issue (05): 716-723. 上一篇    下一篇

研究论文

3-亚甲基苯并吡喃-2,4-二酮与烯醇硅醚的Diels-Alder反应合成3,4- 二氢-2H,5H-吡喃并[3,2-c][1]苯并吡喃-5-酮衍生物

彭大权a,b ; 刘 蕴b ; 吕志锋b; 徐建华*,b   

  1. (a重庆师范大学化学学院 重庆 400047)
    (b南京大学化学化工学院 南京 210093)
  • 收稿日期:2007-09-16 修回日期:2008-10-20 发布日期:2009-05-20
  • 通讯作者: 徐建华

Synthesis of 3,4-Dihydro-2H,5H-pyrano[3,2-c][1]benzopyran-5-one Derivatives by Diels-Alder Reactions of 3-Methylenebenzopyran- 2,4-diones with Silyl Enol Ethers

Peng, Daquan a,b ; Liu, Yun b; Lü, Zhifeng b; Xu, Jianhua*,b   

  1. (a School of Chemistry, Chongqing Normal University, Chongqing 400047)
    (b School of Chemistry & Chemical Engineering, Nanjing University, Nanjing 210093)
  • Received:2007-09-16 Revised:2008-10-20 Published:2009-05-20
  • Contact: Xu, Jianhua

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被引次数

4

通过4-羟基香豆素与苯甲醛、甲醛和戊醛缩合产生的quinone methide与烯醇硅醚的Diels-Alder反应, 以较高产率合成了一系列含有硅氧基的3,4-二氢-2H,5H-吡喃并[3,2-c][1]苯并吡喃-5-酮衍生物. 用X射线单晶衍射确定了其中5个化合物的空间构型. 利用密度泛函(DFT)方法计算反应物之间的前线分子轨道相互作用, 对反应的区域选择性进行了研究, 计算结果与实验值相符.

关键词: 烯醇硅醚, Diels-Alder反应, 吡喃并[3,2-c][1]苯并吡喃, quinone methide

Quinone methides, generated in situ from the reaction of 4-hydroxycoumarin with benzaldehyde, formaldehyde and pentanal, underwent the Diels-Alder reaction with silyl enol ethers to give a series of 3,4-dihydro-2H,5H-pyrano[3,2-c][1]benzopyran derivatives in high yields. Steric configurations of five compounds were determined by X-ray diffraction experiments. The regioselectivity of the reactions was in-vestigated by frontier molecular orbital interactions between the reactants as calculated by a density func-tional theory (DFT) method, which well rationalized the observed data.

Key words: silyl enol ether, Diels-Alder reaction, pyrano[3,2-c][1]benzopyran, quinone methide