title: Mechanistic Study of a Photocatalyzed C-S Bond Formation Involving Alkyl/Aryl Thiosulfate.
abstract: This study presents thioether construction involving alkyl/aryl thiosulfates and diazonium salt catalyzed by visible-light-excited [Ru(bpy)3 Cl2 ] at room temperature in 44-86 % yield. Electron paramagnetic resonance studies found that thiosulfate radical formation was promoted by K2 CO3 . Conversely, radicals generated from BnSH or BnSSBn (Bn=benzyl) were clearly suppressed, demonstrating the special property of thiosulfate in this system. Transient absorption spectra confirmed the electron-transfer process between [Ru(bpy)3 Cl2 ] and 4-MeO-phenyl diazonium salt, which occurred with a rate constant of 1.69×10(9)  M(-1)  s(-1) . The corresponding radical trapping product was confirmed by X-ray diffraction. The full reaction mechanism was determined together with emission quenching data. Furthermore, this system efficiently avoided the over-oxidation of sulfide caused by H2 O in the photoexcited system containing Ru(2+) . Both aryl and heteroaryl diazonium salts with various electronic properties were investigated for synthetic compatibility. Both alkyl- and aryl-substituted thiosulfates could be used as substrates. Notably, pharmaceutical derivatives afforded late-stage sulfuration smoothly under mild conditions.
authors.affiliation: Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 North Zhongshan Rd., Shanghai 200062 (P. R. China).
authors.forename: Yiming
authors.initials: Y
authors.lastname: Li
authors.affiliation: Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 North Zhongshan Rd., Shanghai 200062 (P. R. China).
authors.forename: Weisi
authors.initials: W
authors.lastname: Xie
authors.affiliation: Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 North Zhongshan Rd., Shanghai 200062 (P. R. China). xfjiang@chem.ecnu.edu.cn.|State Key Laboratory of Elemento-organic Chemistry, Nankai University (P. R. China). xfjiang@chem.ecnu.edu.cn.
authors.forename: Xuefeng
authors.initials: X
authors.lastname: Jiang
keywords: bond formation; mechanistic study; organic thiosulfates; pharmaceuticals sulfuration; photocatalysis