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Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4 + 2] Annulation

Authors :
Jayachandran Jayakumar
Chien-Hong Cheng
Shih-Ching Chuang
Mong-Feng Chiou
Source :
The Journal of Organic Chemistry. 83:7814-7824
Publication Year :
2018
Publisher :
American Chemical Society (ACS), 2018.

Abstract

Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (MI/MIII, M = Co and Rh) generally favor a [3 + 2] cyclization pathway, whereas those involving higher oxidation states (MIII/MV) proceed through a [4 + 2] cyclization pathway. A catalytic cycle with novel MIII/MV as a crucial species was successfully revealed for isoquinolinium salts synthesis, in which highly valent MV was encountered not only in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

Details

ISSN :
15206904 and 00223263
Volume :
83
Database :
OpenAIRE
Journal :
The Journal of Organic Chemistry
Accession number :
edsair.doi...........b02146fcadc95f4d683a670926e8be5d
Full Text :
https://doi.org/10.1021/acs.joc.8b00711