Selective Copper Complex-Catalyzed Hydrodefluorination of Fluoroalkenes and Allyl Fluorides: A Tale of Two Mechanisms.
| Autor: | Andrella NO; Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation , 30 Marie Curie , University of Ottawa , Ottawa , ON K1N 6N5 Canada., Xu N; Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation , 30 Marie Curie , University of Ottawa , Ottawa , ON K1N 6N5 Canada., Gabidullin BM; Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation , 30 Marie Curie , University of Ottawa , Ottawa , ON K1N 6N5 Canada., Ehm C; Dipartimento di Scienze Chimiche , Università di Napoli Federico II , Via Cintia 80126 Napoli , Italy., Baker RT; Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation , 30 Marie Curie , University of Ottawa , Ottawa , ON K1N 6N5 Canada. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of the American Chemical Society [J Am Chem Soc] 2019 Jul 24; Vol. 141 (29), pp. 11506-11521. Date of Electronic Publication: 2019 Jul 15. |
| DOI: | 10.1021/jacs.9b03101 |
| Abstrakt: | The transition to more economically friendly small-chain fluorinated groups is leading to a resurgence in the synthesis and reactivity of fluoroalkenes. One versatile method to obtain a variety of commercially relevant hydrofluoroalkenes involves the catalytic hydrodefluorination (HDF) of fluoroalkenes using silanes. In this work it is shown that copper hydride complexes of tertiary phosphorus ligands (L) can be tuned to achieve selective multiple HDF of fluoroalkenes. In one example, HDF of the hexafluoropropene dimer affords a single isomer of heptafluoro-2-methylpentene in which five fluorines have been selectively replaced with hydrogens. DFT computational studies suggest a distinct HDF mechanisms for L |
| Databáze: | MEDLINE |
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