Ruthenium-catalyzed one-pot double allylation/cycloisomerization of 1,3-dicarbonyl compounds leading to exo-methylenecyclopentanes

被引:40
作者
Yamamoto, Y [1 ]
Nakagai, Y [1 ]
Itoh, K [1 ]
机构
[1] Nagoya Univ, Grad Sch Engn, Dept Mol Design & Engn, Nagoya, Aichi 4648603, Japan
关键词
alkenes; allylation; cycloisomerization; homogeneous; catalysis; ruthenium;
D O I
10.1002/chem.200305340
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The ruthenium-catalyzed one-pot double allylation/cycloisomerization of 1,3-diketones and methyl acetoacetate gave exo-methylenecyclopentanes in moderate to good yields with high isomer selectivity. The double allylation step effectively proceeded in the presence of a Ru-II precatalyst, [Cp*RuCl(cod)], in 1,2-dichloroethane at 90degreesC. The subsequent cycloisomerization was carried out upon addition of triethylsilane as a hydride source without purification of a 1,6-diene intermediate. Detailed inspections of the reaction by H-1 NMR spectroscopy disclosed that triethylsilyl methyl ether plays an important role for the conversion of a ruthenium(IV) allyl complex formed in the double allylation step into a ruthenium(II) species required for the cycloisomerization.
引用
收藏
页码:231 / 236
页数:6
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