A combined experimental and computational study of ligand-controlled Chan-Lam coupling of sulfenamides

Kaiming Han, Hong Liu, Madeline E. Rotella, Zeyu Xu, Lizhi Tao, Shufeng Chen (), Marisa C. Kozlowski () and Tiezheng Jia ()
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Kaiming Han: Southern University of Science and Technology, 1088 Xueyuan Blvd., Shenzhen
Hong Liu: Southern University of Science and Technology, 1088 Xueyuan Blvd., Shenzhen
Madeline E. Rotella: University of Pennsylvania, 231 South 34th Street
Zeyu Xu: Southern University of Science and Technology, 1088 Xueyuan Blvd., Shenzhen
Lizhi Tao: Southern University of Science and Technology, 1088 Xueyuan Blvd., Shenzhen
Shufeng Chen: Department of Chemistry and Chemical Engineering, Inner Mongolia University
Marisa C. Kozlowski: University of Pennsylvania, 231 South 34th Street
Tiezheng Jia: Southern University of Science and Technology, 1088 Xueyuan Blvd., Shenzhen

Nature Communications, 2024, vol. 15, issue 1, 1-9

Abstract: Abstract The unique features of the sulfenamides’ S(II)-N bond lead to interesting stereochemical properties and significant industrial functions. Here we present a chemoselective Chan–Lam coupling of sulfenamides to prepare N-arylated sulfenamides. A tridentate pybox ligand governs the chemoselectivity favoring C–N bond formation, and overrides the competitive C-S bond formation by preventing the S,N-bis-chelation of sulfenamides to copper center. The Cu(II)-derived resting state of catalyst is captured by UV-Vis spectra and EPR technique, and the key intermediate is confirmed by the EPR isotope response using 15N-labeled sulfenamide. A computational mechanistic study reveals that N-arylation is both kinetically and thermodynamically favorable, with deprotonation of the sulfenamide nitrogen atom occurring prior to reductive elimination. The origin of ligand-controlled chemoselectivity is explored, with the interaction between the pybox ligand and the sulfenamide substrate controlling the energy of the S-arylation and the corresponding product distribution, in agreement with the EPR studies and kinetic results.

Date: 2024
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DOI: 10.1038/s41467-024-49089-0

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