We report a combined experimental and mechanistic study on the Buchwald–Hartwig amination and C–S/S–H metathesis of aryl sulfides by selective activation of C–S bonds mediated by well-defined, air- and moisture-stable Pd(II)–NHC precatalysts, [Pd(NHC)(μ-Cl)Cl]2. This class of Pd(II)–NHC precatalysts displays excellent activity in the cross coupling of aryl sulfides. Most crucially, we unravel the unified mechanism for activation of C–S bonds in the C–N cross-coupling and C–S metathesis manifolds, where the inert C–S bond serves as a precursor to valuable amine or thioether products.
Bibliographical noteKAUST Repository Item: Exported on 2022-12-15
Acknowledgements: The authors thank Rutgers University, the National Science Foundation (NSF, CAREER CHE-1650766), and the National Institutes of Health (NIH, R35GM133326) for generous financial support. Supplemental funding for this project was provided by the Rutgers University─Newark Chancellor’s Research Office. The 500 MHz spectrometer used in this study was supported by the NSF–Major Research Instrumentation (MRI) grant (CHE-1229030). Albert Poater is a Serra Húnter Fellow, with the ICREA Academia Prize 2019, and thanks the Spanish Ministerio de Ciencia e Innovación for Project PID2021-127423NB-I00. Steven P. Nolan thanks the BOF research fund as well as the SBO projects CO2perate and D2M for financial support. Catherine S. J. Cazin thanks the FWO for support. Luigi Cavallo thanks the University of Girona for sabbatical hospitality.
ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry