Recent Advances in "Formal" Ruthenium-Catalyzed [2+2+2] Cycloaddition Reactions of Diynes to Alkenes

被引：35

作者：

Garcia-Rubin, Silvia ^{[1
]}

Varela, Jesus A. ^{[1
]}

Castedo, Luis ^{[1
]}

Saa, Carlos ^{[1
]}

机构：

[1] Univ Santiago de Compostela, Fac Quim, Dept Quim Organ, Santiago De Compostela 15782, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2008年 / 14卷 / 31期

关键词：

alkenes; catalysis; cycloaddition reactions; cyclohexadienes; diynes; ruthenium;

D O I：

10.1002/chem.200801088

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Fomal and standard Ru-II-catalyzed [2+2+21 cycloaddition of 1.6-diynes to alkenes gave bicyclic 1,3-cyclohexadienes in relatively good yields. When terminal 1,6-diynes 1 were used, two isomeric bicyclic 1,3-cyclohexadienes 4 or 6 were obtained, depending on the acyclic or cyclic nature of the alkene partner. When unsymmetrical substituted 1,6-diynes 7 were used, the reaction with acyclic alkenes took place regio- and stereoselectively to afford bicyclic 1,3-cyclohexadienes 8. A cascade process that behaves as a "formal" Ru-II-catalyzed [2+2+2] cyclo-addition explained these results. Initially a Ru-catalyzed linear coupling of 1,6-diynes 1 and 7 with acyclic alkenes occurs to give open 1,3,5-trienes of type 3, which after a thermal disrotatory 6e(-)pi-electrocyclization led to the final 1,3-cyclohexadienes 4 and 8. When disubstituted 1,6-diyne 10 was used with electron-deficient alkenes, new exo-methylene cyclohexadienes 12 arose from it competitive reaction path-way.

引用

页码：9772 / 9778

页数：7

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