Control of London Dispersion Interactions in Metal-Catalyzed C-H Activation
Final Report Abstract
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.
Publications
- 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at https://doi.org/10.1021/acs.orglett.1c00615)
