Formal aromatic C-H insertion for stereoselective isoquinolinone synthesis and studies on mechanistic insights into the C-C bond formation.
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.
Park
Chan Pil
CP
Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, California 90089-1661, USA.
Nagle
Advait
A
Yoon
Cheol Hwan
CH
Chen
Chiliu
C
Jung
Kyung Woon
KW
D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003979:Diazonium Compounds / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D007546:Isoquinolines / Q000138:chemical synthesis* / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
D003979:Diazonium Compounds; D007546:Isoquinolines; C011752:diazoacetamide; D002244:Carbon; D006859:Hydrogen; D012238:Rhodium; C039109:isoquinoline; C032111:diazoacetic ester