title: Synthesis of di-, tri-, and tetrasulfides through multifold carbon-sulfur cross-coupling reactions with indium tri(organothiolates) in a one-pot procedure.
abstract: Pd-catalyzed multifold (2-, 3-, and 4-fold) carbon-sulfur cross-coupling reaction of indium tri(organothiolates) with polybromonated aromatic and heteroaromatic compounds was developed in a one-pot procedure. Both 2,5-dibromopyridine and 2,6-dibromopyridine reacted with indium tri(organothiolates) (0.68 equiv) in the presence of 4 mol % of Pd(OAc)(2), 4.2 mol % of Xantphos, and 1 equiv of diisopropylethylamine (DIPEA), producing disulfides in good to excellent yields. These results indicate that indium tri(organothiolates) transfer all three alkyl- or arylthio groups attached to indium metal to electrophilic coupling partners. Indium tri(organothiolates) derived from alkyl thiol having a low boiling point, such as n-propyl, isopropyl, and tert-butyl thiol, acted as good nucleophilic coupling partners. In addition, indium tri(arylthiolates) derived from aryl thiols possessing an electron-withdrawing or -donating group on the aromatic ring participated well in the Pd-catalyzed multifold carbon-sulfur cross-coupling reaction. 4,4'-Dibromo-1,1'-biphenyl, 9,10-dibromoanthracene, 2,4-dibromoanisole, 2,7-dibromo-9,9-dimethylfluorene, 3,4-dibromothiophene, 2,3-dibromothiophene, 2,2'-bithiophene, 1,3,5-tribromobenzene, and 1,2,4,5-tetrabromobenzene were converted smoothly to the corresponding di-, tri-, and tetrasulfides.
authors.affiliation: Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University, Chuncheon, Republic of Korea. phlee@kangwon.ac.kr
authors.forename: Phil Ho
authors.initials: PH
authors.lastname: Lee
authors.forename: Youngchul
authors.initials: Y
authors.lastname: Park
authors.forename: Sangkyun
authors.initials: S
authors.lastname: Park
authors.forename: Euijae
authors.initials: E
authors.lastname: Lee
authors.forename: Sunggak
authors.initials: S
authors.lastname: Kim
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003432:Cross-Linking Reagents / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D007204:Indium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013440:Sulfides / Q000138:chemical synthesis* / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
chemical_list: D003432:Cross-Linking Reagents; D006571:Heterocyclic Compounds; D006842:Hydrocarbons, Brominated; D013440:Sulfides; D007204:Indium; D013455:Sulfur; D002244:Carbon