Formal Aromatic C−H Insertion for Stereoselective Isoquinolinone Synthesis and Studies on Mechanistic Insights into the C−C Bond Formation

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• 作者：Chan Pil Park ; Advait Nagle ; Cheol Hwan Yoon ; Chiliu Chen ; Kyung Woon Jung
• 刊名：Journal of Organic Chemistry
• 出版年：2009
• 出版时间：August 21, 2009
• 年：2009
• 卷：74
• 期：16
• 页码：6231-6236
• 全文大小：830K
• 年卷期：v.74,no.16(August 21, 2009)
• ISSN：1520-6904

文摘

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.