Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, California 90089-1661, USA.
J Org Chem. 2009 Aug 21;74(16):6231-6. doi: 10.1021/jo9011255.
Formal aromatic C-H insertion of rhodium(II) carbenoid was intensively investigated to develop a new methodology and probe its mechanism. Contrasting with the previously proposed direct C-H insertion, the mechanism was revealed to be electrophilic aromatic substitution, which was supported by substituent effects on the aromatic ring and a secondary deuterium kinetic isotope effect. Various isoquinolinones were synthesized intramolecularly via six-membered ring formation with high regio- and diastereoselectivity, while averting the common Buchner-type reaction. Intermolecularly, dirhodium catalyzed formal aromatic C-H insertion on electron-rich aromatics was also achieved.
我们深入研究了铑(II)碳烯的形式芳族 C-H 插入反应，以开发新的方法并探究其机理。与先前提出的直接 C-H 插入反应相反，该机理被揭示为亲电芳香取代反应，这得到了芳环取代基效应和次级氘动力学同位素效应的支持。通过六元环形成，各种异喹啉酮以高区域和立体选择性进行分子内合成，同时避免了常见的布赫纳型反应。在分子间，二铑催化的富电子芳环的形式芳族 C-H 插入反应也得以实现。
