Kontrolle der London Dispersionswechselwirkungen in der Metall-katalysierten C-H-Aktivierung
Zusammenfassung der Projektergebnisse
We studied the effect of attractive London dispersion energy interactions on various C–H activations. Within our studies, we unraveled the importance of attractive noncovalent interactions on stabilizing key intermediates and transition states and successfully devised highly chemo-, site- and enantio-selective catalyzed C–H activations. We inter alia developed enantioselective ruthenium- and nickel-catalyzed C–H activations, enabled by the tailored design of secondary phosphine oxides and novel chiral carboxylic acids. Detailed studies of the siteselectivity in ruthenium-catalyzed direct C–H alkylation with secondary alkylhalides provided rational for the observed selectivities and the chemoselectivity determining factors in ruthenium-catalyzed oxidative C–H/C–H coupling versus the direct arylation have been identified.
Projektbezogene Publikationen (Auswahl)
- Cobalt-Catalyzed C–H Cyanations: Insights into the Reaction Mechanism and the Role of London Dispersion. Beilstein J. Org. Chem. 2018, 14, 1537-1545
E. Detmar, V. Müller, D. Zell, L. Ackermann, M. Breugst
(Siehe online unter https://doi.org/10.3762/bjoc.14.130) - Distal Weak Coordination of Acetamides in Ruthenium(II)-Catalyzed C–H Activation Processes. Angew. Chem. Int. Ed. 2018, 57, 765-768
Q. Bu, T. Rogge, V. Kotek, L. Ackermann
(Siehe online unter https://doi.org/10.1002/anie.201711108) - Arene-Free Ruthenium(II/IV)-Catalyzed Bifurcated Arylation for Oxidative C–H/C–H Functionalizations. Angew. Chem. Int. Ed. 2019, 58, 15640-15645
T. Rogge, L. Ackermann
(Siehe online unter https://doi.org/10.1002/anie.201909457) - Enantioselective Aluminum-Free Alkene Hydroarylations via C–H Activation by a Chiral Nickel/JoSPOphos Manifold. Angew. Chem. Int. Ed. 2019, 58, 1749-1753
J. Loup, V. Müller, D. Ghorai, L. Ackermann
(Siehe online unter https://doi.org/10.1002/anie.201813191) - Rhodaelectrocatalysis for Annulative C–H Activation: Polycyclic Aromatic Hydrocarbons by Versatile Double Electrocatalysis. Angew. Chem. Int. Ed. 2019, 58, 6342-6346
W.-J. Kong, L. H. Finger, J. C. A. Oliveira, L. Ackermann
(Siehe online unter https://doi.org/10.1002/anie.201901565) - Reactivity-Controlling Factors in Carboxylate-Assisted C–H Activation under 4d and 3d Transition Metal Catalysis. ACS Catal. 2020, 10, 10551-10558
T. Rogge, J. C. A. Oliveira, R. Kuniyil, L. Hu, L. Ackermann
(Siehe online unter https://doi.org/10.1021/acscatal.0c02808) - Regiodivergent C–H and Decarboxylative Alkylation by Ruthenium Catalysis: ortho versus meta Position-Selectivity. Angew. Chem. Int. Ed. 2020, 59, 18795-18803
K. Korvorapun, M. Moselage, J. Struwe, T. Rogge, A. M. Messinis, L. Ackermann
(Siehe online unter https://doi.org/10.1002/anie.202007144) - Enantioselective Ruthenium-Catalyzed C–H Alkylations by a Chiral Carboxylic Acid with Attractive Dispersive Interactions. Org. Lett. 2021, 23, 2760–2765
U. Dhawa, R. Connon, J. C. A. Oliveira, R. Steinbock, L. Ackermann
(Siehe online unter https://doi.org/10.1021/acs.orglett.1c00615)
