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DFT Studies on the Dirhodium-Catalyzed [3 + 2] and [3 + 3] Cycloaddition Reactions of Enol Diazoacetates with Isoquinolinium Methylide: Mechanism, Selectivity, and Ligand Effect.
- Source :
-
Organometallics . 5/14/2018, Vol. 37 Issue 9, p1373-1380. 8p. - Publication Year :
- 2018
-
Abstract
- The reaction mechanisms of dirhodium-catalyzed [3 + 2] and [3 + 3] cycloaddition between enol diazoacetate and isoquinolinium methylide have been studied in detail using density functional theory and a solution-phase translational entropy model. The reaction starts with the formation of a metallic carbene intermediate first, from which two competing reaction channels of [3 + 2] and [3 + 3] cycloaddition take place. For CAT1-catalyzed reactions, the calculated activation free energy barriers for [3 + 3] and [3 + 2] cycloaddition reactions are 14.3 and 16.0 kcal mol-1, respectively, which is in good agreement with the ratio of products. Both the steric and electronic effects have been considered for CAT2- and CAT3-catalyzed reactions, with which the ratio of products has also been rationalized. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 02767333
- Volume :
- 37
- Issue :
- 9
- Database :
- Academic Search Index
- Journal :
- Organometallics
- Publication Type :
- Academic Journal
- Accession number :
- 129637468
- Full Text :
- https://doi.org/10.1021/acs.organomet.8b00069