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
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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
Bu, Qingqing; Rogge, Torben; Kotek, Vladislav & Ackermann, Lutz
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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
Detmar, Eric; Müller, Valentin; Zell, Daniel; Ackermann, Lutz & Breugst, Martin
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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
Rogge, Torben & Ackermann, Lutz
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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
Loup, Joachim; Müller, Valentin; Ghorai, Debasish & Ackermann, Lutz
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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
Kong, Wei‐Jun; Finger, Lars H.; Oliveira, João C. A. & Ackermann, Lutz
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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
Rogge, Torben; Oliveira, João C. A.; Kuniyil, Rositha; Hu, Lianrui & Ackermann, Lutz
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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
Korvorapun, Korkit; Moselage, Marc; Struwe, Julia; Rogge, Torben; Messinis, Antonis M. & Ackermann, Lutz
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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
Dhawa, Uttam; Connon, Robert; Oliveira, João C. A.; Steinbock, Ralf & Ackermann, Lutz
