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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
- 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