Noble applications of abundant metals: Asymmetric Co, Ni, Fe and Mn-catalyzed C-H activation

• Applicant: Professor Dr. Lutz Ackermann
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2017 to 2021
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 391136690

• Final Report Year: 2021

Final Report Abstract

Within this project, we devised transition metal-catalyzed highly enantioselective C–H activations. Thus, sustainable cobalt-catalyzed C–H activation permitted the efficient construction of chiral heterocycle motifs including the synthesis of atropisomeric heterobiaryls. The C–H alkylation and arylation were enabled by the design of novel chiral ligands based on carboxylic acids and adamantyl-substituted N-heterocyclic carbenes, respectively. Enantioselective Electrocatalysis was realized in terms of asymmetric C−H activation through transient directing groups with easily-accessible amino acids. Thus, enantiomerically enriched heterobiaryls were achieved by palladaelectro-catalyzed olefination.

Publications

• Enantioselective Cobalt(III)-Catalyzed C–H Activation Enabled by Chiral Carboxylic Acid Cooperation. Angew. Chem. Int. Ed. 2018, 57, 15425-15429
  F. Pesciaioli, U. Dhawa, J. C. A. Oliveira, R. Yin, M. John, L. Ackermann
  (See online at https://doi.org/10.1002/anie.201808595)
• Enantioselective C-H Activation with Earth-Abundant 3d Transition Metals. Angew. Chem. Int. Ed. 2019, 58, 12803-12818
  J. Loup, U. Dhawa, F. Pesciaioli, J. Wencel-Delord, L. Ackermann
  (See online at https://doi.org/10.1002/anie.201904214)
• Enantioselective Palladaelectro‐Catalyzed C–H Activations by Transient Directing Groups: Expedient Access to Helicenes. Angew. Chem. Int. Ed. 2020, 59, 13451-13457
  U. Dhawa, C. Tian, T. Wdowik, J. C. A. Oliveira, J. Hao, L. Ackermann
  (See online at https://doi.org/10.1002/anie.202003826)
• Enantioselective Palladaelectro-Catalyzed C–H Olefinations and Allylations for N–C Axial Chirality. Chem. Sci. 2021, 12, 14182-14188
  U. Dhawa, T. Wdowik, X. Hou, B.Yuan, J. C. A. Oliveira, L. Ackermann
  (See online at https://doi.org/10.1039/d1sc04687j)