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Carbon-carbon bond formation lies at the centre of building molecular complexity. Transition metal catalysis has been revolutionary for that purpose capitalizing on organometallic reactivities. However, two-electron-pathways have their limitations due to the classical electronic constraints, which has been greatly complemented in the last decade by various one-electron-species, mainly carbon-centred free radicals. In this seminar, we will witness different ways of generating aromatic as well as aliphatic carbon-centred radicals via the cleavage of C-H, [1-3] C-F [4] and C-I [5] bonds. The methodologies are unique in each case and vary from transition metal-free electron-catalyzed chain reactions to metallaphotoredox catalysis and electron donor-acceptor (EDA) complex photoactivation. The rational development of each method will be discussed along with the exploration of their scope and synthetic utilities. Detailed mechanistic investigations for each case will also be presented to showcase the versatile reactivities of carbon-centred radicals.
[1] Dewanji, A.; van Dalsen, L.; Rossi-Ashton, J. A.; Gasson, E.; Crisenza, G. E. M.; Procter, D. J. Nat. Chem. 2023, 15, 43 – 52; [2] Dewanji, A.; Krach, P. E.; Rueping, M. Angew. Chem. Int. Ed. 2019, 58, 3566 – 3570; [3] Krach, P. E.; Dewanji, A.; Yuan, T.; Rueping, M. Chem. Commun. 2020, 56, 6082 – 6085; [4] Dewanji, A.; Bülow, R. F.; Rueping, M. Org. Lett. 2020, 22, 1611 – 1617; [5] Dewanji, A.; Murarka, S.; Curran, D. P.; Studer, A. Org. Lett. 2013, 15, 6102 – 6105. |