Ru 3 (CO) 12 -catalyzed divergent ring-opening coupling reactions of a cyclopropenone with methyl acrylate (an electron-deficient alkene) are developed. Under an argon atmosphere, a decarbonylative linear codimer is obtained, while cyclopentenones are obtained under carbon monoxide (20 atm) without decarbonylation. While ruthenium complexes show no catalytic activity for the ring-opening cocyclization of cyclopropenones with ethylene (20 atm) or bicyclo[2.2.1]hept-2-ene (2-norbornene), rhodium complexes, especially [RhCl(η 4 -1,5-cod)] 2 , show high catalytic activity for the desired cocyclization reactions to give the corresponding cyclopentenones in high yields and selectivities. In addition, [RhCl(η 4 -1,5-cod)] 2 realizes the catalytic ring-opening co­cyclization of cyclopropenones with internal alkynes to give the corresponding cyclopentadienones. In all these reactions, ruthena- or rhodacyclobutenones are considered to be key intermediates, generated by strain-driven oxidative addition of a cyclopropenone C–C bond to an ­active ruthenium or rhodium species.

中文翻译：

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钌和铑催化的环丙烯酮与烯烃或炔烃的开环偶联反应

开发了 Ru 3 (CO) 12 催化的环丙烯酮与丙烯酸甲酯（一种缺电子烯烃）的发散开环偶联反应。在氩气气氛下，获得脱羰线性共二聚体，而在一氧化碳 (20 atm) 下获得环戊烯酮，无需脱羰。虽然钌配合物对环丙烯酮与乙烯 (20 atm) 或双环 [2.2.1] 庚-2-烯 (2-降冰片烯) 的开环共环化没有催化活性，但铑配合物，尤其是 [RhCl(η 4 -1 ,5-cod)] 2 对所需的共环化反应显示出高催化活性，以高产率和选择性得到相应的环戊烯酮。此外，[RhCl(η 4 -1, 5-cod)] 2 实现了环丙烯酮与内部炔烃的催化开环共环化反应得到相应的环戊二烯酮。在所有这些反应中，钌或铑环丁烯酮被认为是关键中间体，由环丙烯酮 C-C 键与活性钌或铑物质的应变驱动氧化加成生成。