| Autor: |
Thomas Louis-Goff, Huu Vinh Trinh, Eileen Chen, Arnold L. Rheingold, Christian Ehm, Jakub Hyvl |
| Přispěvatelé: |
Louis-Goff, T., Trinh, H. V., Chen, E., Rheingold, A. L., Ehm, C., Hyvl, J. |
| Rok vydání: |
2022 |
| Předmět: |
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| Zdroj: |
ACS Catalysis. 12:3719-3730 |
| ISSN: |
2155-5435 |
| DOI: |
10.1021/acscatal.1c05959 |
| Popis: |
An efficient, catalytic difluorocarbenation of olefins to give 1,1-difluorocyclopropanes is presented. The catalyst, an organobismuth complex, uses TMS-CF3 as a stoichiometric difluorocarbene source. We demonstrate both the viability and robustness of this reaction over a wide range of alkenes and alkynes, including electron-poor alkenes, to generate the corresponding 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes. Ease of catalyst recovery from the reaction mixture is another attractive feature of this method. In-depth experimental and theoretical studies show that the key difluorocarbene-generating step proceeds through a bismuth nonredox synchronous mechanism generating highly reactive free CF2 in an endergonic pre-equilibrium. The reversible difluorocarbene generation-and thus low concentration of active species-leads to high selectivity while minimizing CF2-recombination side reactions. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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