607-53-4Relevant articles and documents
Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions
Bouchet, Lydia M.,Pe?é?ory, Alicia B.,Pierini, Adriana B.,Argüello, Juan E.
, p. 5035 - 5042 (2019/06/17)
The reactivity of sulfur- and selenium-centered nucleophiles toward 1-naphthyl radicals was studied in dimethylsulfoxide. The photostimulated reaction of sulfide anions, -SC(NH)C6H5 (1), -SC(NH)NH2 (2), and -SC(NH)CH3 (3), renders, after the addition of MeI, methyl 1-naphthylsulfide as a main product together with bis(1-naphthyl) sulfide and naphthalene under irradiation. Concordantly, the reaction of selenide anions, -SeC(NH)C6H5 (4), -SeC(NH)NH2 (5), and -SeCN (6), produces methyl 1-naphthyl selenide, bis(1-naphthyl) selenide, and naphthalene in the presence of potassium tert-butoxide anion (entrainment conditions). Absolute rate constants for the coupling of ions 1-6 to 1-naphthyl radicals were determined; as a general trend, the selenide-centered nucleophiles enhance in 2 times the reactivity of their sulfide analogues. From the mechanistic study, it is proposed that the unstable radical anion produced by the addition of the nucleophile to 1-naphthyl radical affords, after fragmentation, 1-naphthylsulfide/selenide anion. In addition, experimental results are discussed in terms of density functional theory calculations. There is a generally good agreement between the experimental and the calculated reactivities, the spin density being the main parameter to describe the difference found among the anions under study. Moreover, the calculations predict that anion -SeC(NH)CH3 (7) would be a good candidate for the synthesis of selenide derivatives.
Highly efficient and functional-group-tolerant catalysts for the palladium-catalyzed coupling of aryl chlorides with thiols
Fernandez-Rodriguez, Manuel A.,Shen, Qilong,Hartwig, John F.
, p. 7782 - 7796 (2007/10/03)
The cross-coupling reaction of aryl chlorides with aliphatic and aromatic thiols catalyzed by palladium complexes of the strongly binding bisphosphine CyPF-tBu ligand (1) is reported. Most of the reactions catalyzed by complexes of ligand 1 occur with turnover numbers that exceed those of previous catalysts by two orders of magnitude. The reactions occur with excellent yields, broad scope and high tolerance of functional groups. Coupling of aryl halides with thiols in the presence of low loadings of catalysts derived from other Josiphos type ligands, as well as ligands of other structural types, are also described.
One-Pot Two-Step Synthesis of Aryl Sulfur Compounds by Photoinduced Reactions of Thiourea Anion with Aryl Halides
Argueello, Juan E.,Schmidt, Luciana C.,Penenory, Alicia B.
, p. 4133 - 4136 (2007/10/03)
(Equation presented) The photoinduced reactions of aryl halides with the thiourea anion afford arene thiolate ions in DMSO. These species without isolation, and by a subsequent aliphatic nucleophilic substitution, S RN1 reaction, oxidation, or protonation, yield aryl methyl sulfides, diaryl sulfides, diaryl disulfides, and aryl thiols with good yields (50-80%). This is a simple and convenient approach which involves the use of the commercially available and inexpensive thiourea in a one-pot two-step process for the synthesis of aromatic sulfur compounds.
