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)
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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
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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
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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
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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
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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
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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
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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
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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
