期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 80, 期 20, 页码 10317-10333出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.5b01954
关键词
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资金
- JSPS KAKENHI [26860008]
- Grants-in-Aid for Scientific Research [26860008] Funding Source: KAKEN
Various nitrogen-bridged bicyclic skeletons are found in bioactive natural products and pharmaceuticals. The development of a new reaction to construct these molecular frameworks has attracted considerable attention in synthetic organic chemistry. We developed a novel synthetic method for obtaining a wide variety of nitrogen-bridged bicyclic compounds with a catalytic process, Rh-catalyzed formal carbenoid insertion into an amide C-N bond. Using 0.1-0.4 mol % Rh-2((NHCOBu)-Bu-t)(4) catalyst, various azabicydo[X.Y.Z]alkane derivatives were obtained in good to excellent yield, successfully demonstrating the broad substrate scope of the developed process. Experimental and computational studies to elucidate the reaction mechanism revealed that the formal insertion reaction of a carbenoid into an amide C-N bond proceeded via the formation of Rh-associated N-ylides, followed by an acyl group-selective Stevens [1,2]-shift through a concerted addition/elimination process on the sp(2)-hybridized carbon.
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