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

Han，Kaiming1,2; Liu，Hong1; Rotella，Madeline E.3; Xu，Zeyu1; Tao，Lizhi1; Chen，Shufeng2; Kozlowski，Marisa C.3; Jia，Tiezheng1,4

2024-12-01

10.1038/s41467-024-49089-0

Nature Communications   影响因子和分区

2041-1723

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 N-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.

英语

NI期刊

第一 ; 通讯

2-s2.0-85195252917

Scopus

1.Research Center for Chemical Biology and Omics Analysis,Department of Chemistry,Southern University of Science and Technology,1088 Xueyuan Blvd.,Shenzhen,Guangdong,China
2.Inner Mongolia Key Laboratory of Fine Organic Synthesis,Department of Chemistry and Chemical Engineering,Inner Mongolia University,Hohhot,China
3.Roy and Diana Vagelos Laboratories,Department of Chemistry,University of Pennsylvania,231 South 34th Street,Philadelphia,United States
4.State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin,China

Han，Kaiming,Liu，Hong,Rotella，Madeline E.,et al. A combined experimental and computational study of ligand-controlled Chan-Lam coupling of sulfenamides[J]. Nature Communications,2024,15(1).

Han，Kaiming.,Liu，Hong.,Rotella，Madeline E..,Xu，Zeyu.,Tao，Lizhi.,...&Jia，Tiezheng.(2024).A combined experimental and computational study of ligand-controlled Chan-Lam coupling of sulfenamides.Nature Communications,15(1).

Han，Kaiming,et al."A combined experimental and computational study of ligand-controlled Chan-Lam coupling of sulfenamides".Nature Communications 15.1(2024).