Site‐Selective C−S Bond Formation at C−Br over C−OTf and C−Cl Enabled by an Air‐Stable, Easily Recoverable, and Recyclable Palladium(I) Catalyst. (20th August 2018)

• Record Type: Journal Article
• Authors: Scattolin, Thomas; Senol, Erdem; Yin, Guoyin; Guo, Qianqian; Schoenebeck, Franziska
• Is Part Of: Angewandte Chemie. Volume 130:Number 38(2018)
• Page Start: 12605
• Page End: 12609
• Publication Date: 2018-08-20
• Subjects: Chemoselektivität -- Homogene Katalyse -- Palladium -- Thiolierung -- Zweikernige Katalysatoren; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201806036
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: This report widens the repertoire of emerging Pd I catalysis to carbon–heteroatom, that is, C−S bond formation. While Pd 0 ‐catalyzed protocols may suffer from the formation of poisonous sulfide‐bound off‐cycle intermediates and lack of selectivity, the mechanistically diverse Pd I catalysis concept circumvents these challenges and allows for C−S bond formation (S–aryl and S–alkyl) of a wide range of aryl halides. Site‐selective thiolations of C−Br sites in the presence of C−Cl and C−OTf were achieved in a general and a priori predictable fashion. Computational, spectroscopic, X‐ray, and reactivity data support dinuclear Pd I catalysis to be operative. Contrary to air‐sensitive Pd 0, the active Pd I species was easily recovered in the open atmosphere and subjected to multiple rounds of recycling.