Development of novel reactions using ruthenium carbene catalyst and its application to novel methods for preparing nitrogen-containing heterocycles

被引:51
作者
Arisawa, M
Terada, Y
Theeraladanon, C
Takahashi, K
Nakagawa, M
Nishida, A
机构
[1] Chiba Univ, Grad Sch Pharmaceut Sci, Inage Ku, Chiba 2638522, Japan
[2] Kanagawa Univ, Fac Sci, Dept Chem, Kanagawa 2591293, Japan
关键词
ruthenium carbene; heterocycles; metathesis; olefin isomerization; cycloisomerization;
D O I
10.1016/j.jorganchem.2005.07.029
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of N-allyl-orth.9-vinylaniline with ruthenium carbene catalyst at 50 degrees C gives substituted 1,2-dihydroquinoline through ring-closing metathesis (RCM), which is easily converted to the corresponding quinoline after deprotection. In sharp contrast, when vinyloxytrimethylsilane is added to this reaction mixture, 1,2-dihydroquinoline is not formed and selective isomerization of N-allyl-ortho-vinylaniline is observed at 50 degrees C to give corresponding enamide, which is successfully converted to indole derivative by RCM. The same catalyst system provide indoline derivative at 160 degrees C by cycloisomerization. Based on a detailed mechanistic study, it becomes clear that a ruthenium carbene catalyst, which is highly effective for RCM, reacts with an electron-rich terminal olefin selectively, and another ruthenium species, which effectively catalyzes the isomerization of terminal olefin and cycloisomerization of alpha, omega-diene, is generated. (c) 2005 Elsevier B.V. All rights :reserved.
引用
收藏
页码:5398 / 5406
页数:9
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