Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 45, Pages 16059-16065Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502951
Keywords
bond formation; mechanistic study; organic thiosulfates; pharmaceuticals sulfuration; photocatalysis
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Funding
- NBRPC (973 Program) [2015CB856600]
- NSFC [21472050, 21272075]
- NCET [120178]
- DFMEC [20130076110023]
- Fok Ying Tung Education Foundation [141011]
- program for Shanghai Rising Star [15A1401800]
- Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning
- Changjiang Scholar and Innovative Research Team in University
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This study presents thioether construction involving alkyl/aryl thiosulfates and diazonium salt catalyzed by visible-light-excited [Ru(bpy)(3)Cl-2] at room temperature in 44-86% yield. Electron paramagnetic resonance studies found that thiosulfate radical formation was promoted by K2CO3. 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)Cl-2] and 4-MeO-phenyl diazonium salt, which occurred with a rate constant of 1.69x10(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 H2O in the photoexcited system containing Ru2+. 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.
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