Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids Cong Wang 1 , Hui Zhang 1 , Lucille A. Wells 3 , Tian Liu 2 , Tingting Meng 1 , Qingchao Liu 2 , Patrick J. Walsh, 3 Marisa C. Kozlowski 3* , Tiezheng Jia 1 1 Southern University of Science and Technology, China, 2 Northwest University, China, 3 University of Pennsylvania, USA In recent years, N- Arylation of NH -sulfoximines represents an appealing approach to access N- aryl sulfoximines because of the distinctive structural motifs in biological and medicinal chemistry, 1,2 but has not been successfully applied to NH -diaryl sulfoximines. 3 Herein, an unprecedented copper-catalyzed photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids is described (Scheme 1). Mechanistic investigations also reveal a unique autocatalysis process. This neutral and ligand-free coupling is initiated by ambient light-induced copper-catalyzed single-electron reduction of NH -sulfoximines. The C-N coupling products, N- arylated sulfoximines, serve as ligands to bind to the copper species, generating the photocatalyst. Furthermore, dihydrogen gas was detected as a byproduct. The thermodynamics and pathways of key steps were calculated using Gaussian 16. 4 The protocol described herein represents a novel alternative strategy to the classic oxidative Chan-Lam reaction. This work is published at Nat. References 1. (a) Lucking, U. Chem. Int. Ed. 2013, 52 , 9399-408. (b) Frings, M., Bolm, C., Blum, A.; Gnamm, C. Eur. J. Med. Chem. 2017, 126 , 225-245. 2. Siemeister, G.; Lucking, U.; Wengner, A. M.; Lienau, P.; Steinke, W.; Schatz, C.; Mumberg, D.; Ziegelbauer, K. BAY 1000394, Cancer Ther. 2012, 11 , 2265-73. 3. (a) Bachon, A. K., Steinkamp, A.D., Bolm, C. Synth. Catal. 2018, 360 , 1088-1093. (b) Wimmer, A., Konig, B., Adv. Synth. Catal. 2018, 360 , 3277-3285.Frisch, M. J.,et al. Gaussian 16 , Revision B.01; Gaussian, Inc.: Wallingford, CT, 2016. 4. Wang, C.; Zhang, H.; Wells, L. A.; Liu, T.; Meng, T.; Liu, Q.; Walsh, P. J.; Kozlowski, M. C.; Jia, T. Nat. Commun. 2021 , 12 , 932.
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