Design und Synthese starker pi-Akzeptor-Liganden und ihre Anwendung in der Au(I)- und Pt(II)-Katalyse sowie Naturstoffsynthese
Zusammenfassung der Projektergebnisse
Over the past several years and thanks to the research project, we have demonstrated that a-cationic phosphines of different structures can be easily synthesized and effectively employed as ancillary ligands. Due to their strong acceptor properties, these ligands efficiently accept electron density from the metal centers they coordinate and, for this reason, they facilitate catalytic cycles requiring strong Lewis acidity at the metal center during the rate determining step. This has been efficiently exploited in our group in the framework of Au(I) and Pt(II)-catalysis. α-Cationic arsines have also been prepared; they have found to depict even enhanced acceptor properties than these of their lighter analogues. We anticipate that the intensive acceleration effects observed in π-acid catalysis by the use of α-cationic phosphines might have tremendous implications in the area of asymmetric catalysis, where catalysts able to work at lower temperatures are usually required to obtain good enantiomeric excess. The profitable employment of a-cationic phosphines beyond π-acid catalysis is another challenge still remaining in this area. We look forward to addressing both of these in the near future; in fact this is the main topic of the most recent application to the DFG.
Projektbezogene Publikationen (Auswahl)
- "Bis- and Tris(pyrazolyl)borate/Methane-Stabilized PIII-Centered Cations." Chem.–Eur. J. 2014, 20, 8575- 8578
L. Gu, G. Gopakumar, P. Gualco, W. Thiel, M Alcarazo
(Siehe online unter https://doi.org/10.1002/chem.201402636) - "Synthese, Struktur und Anwendungen von Pyridiniumphosphanen." Angew. Chem. 2014, 126, 8877-8881. "Synthesis, Structure, and Applications of Pyridiniophosphines." Angew. Chem. Int. Ed. 2014, 53, 8732-8736
H. Tinnermann, C. Wille, M. Alcarazo
(Siehe online unter https://doi.org/10.1002/ange.201401073) - "α-Cationic Phosphines: Synthesis and Applications." Chem.–Eur. J. 2014, 20, 7868-7877
M. Alcarazo
(Siehe online unter https://doi.org/10.1002/chem.201402375) - "Bis[(dialkylamino)cyclopropenimine]-Stabilized PIII- and PV-Centered Dications." Chem.–Eur. J. 2015, 21, 10829-10834
Á. Kozma, J. Rust, M. Alcarazo
(Siehe online unter https://doi.org/10.1002/chem.201500688) - "Bis(cyclopropenium)phosphines: Synthesis, Reactivity, and Applications." Chem. Eur. J. 2016, 22, 15320-15327
G. Mehler, P. Linowski, J. Carreras, A. Zanardi, J. W. Dube, M. Alcarazo
(Siehe online unter https://doi.org/10.1002/chem.201601759) - "Synthesis and Reactivity of α-Cationic Phosphines: The Effect of Imidazolinium and Amidinium Substituents." Dalton Trans. 2016, 45, 1872-1876
E. Haldón, Á. Kozma, H. Tinnermann, L. Gu, R. Goddard, M. Alcarazo
(Siehe online unter https://doi.org/10.1039/C5DT02341F)
