Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids

Cong Wang, Hui Zhang, Lucille A. Wells, Tian Liu, Tingting Meng, Qingchao Liu, Patrick J. Walsh, Marisa C. Kozlowski () and Tiezheng Jia ()
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Cong Wang: Southern University of Science and Technology
Hui Zhang: Southern University of Science and Technology
Lucille A. Wells: University of Pennsylvania
Tian Liu: Northwest University
Tingting Meng: Southern University of Science and Technology
Qingchao Liu: Northwest University
Patrick J. Walsh: University of Pennsylvania
Marisa C. Kozlowski: University of Pennsylvania
Tiezheng Jia: Southern University of Science and Technology

Nature Communications, 2021, vol. 12, issue 1, 1-11

Abstract: Abstract N-Arylation of NH-sulfoximines represents an appealing approach to access N-aryl sulfoximines, but has not been successfully applied to NH-diaryl sulfoximines. Herein, a copper-catalyzed photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids is described. This neutral and ligand-free coupling is initiated by ambient light-induced copper-catalyzed single-electron reduction of NH-sulfoximines. This electron transfer route circumvents the sacrificial oxidant employed in traditional Chan-Lam coupling reactions, increasing the environmental friendliness of this process. Instead, dihydrogen gas forms as a byproduct of this reaction. Mechanistic investigations also reveal a unique autocatalysis process. The C–N coupling products, N-arylated sulfoximines, serve as ligands along with NH-sulfoximine to bind to the copper species, generating the photocatalyst. DFT calculations reveal that both the NH-sulfoximine substrate and the N-aryl product can ligate the copper accounting for the observed autocatalysis. Two energetically viable stepwise pathways were located wherein the copper facilitates hydrogen atom abstraction from the NH-sulfoximine and the ethanol solvent to produce dihydrogen. The protocol described herein represents an appealing alternative strategy to the classic oxidative Chan-Lam reaction, allowing greater substrate generality as well as the elimination of byproduct formation from oxidants.

Date: 2021
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DOI: 10.1038/s41467-021-21156-w

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