Nickel-Catalyzed Direct Cross-Coupling of Diaryl Sulfoxide with Aryl Bromide

Abstract

The direct cross-couplings of diaryl sulfoxides with aryl bromides via C–S bond cleavage could be readily accomplished using nickel­(II) as the catalyst, 1,2-bis­(diphenylphosphino)­ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF, leading to the corresponding biaryls in moderate to good yields. The reaction exhibited a broad substrate scope and could be applied to a gram-scale synthesis. The “one-pot” reaction, which avoids the utility of presynthesized and moisture-labile organometallic compounds, is operationally simple and step-economic.

Hydroxylation of Aryl Sulfonium Salts for Phenol Synthesis under Mild Reaction Conditions

“…Although the hydroxylation of aryl thianthrenium salts have been accomplished by using water as hydroxide source, the reaction should be conducted under photoredox conditions in the presence of Ir and Cu catalysts [ 74 ]. In the continuation of our efforts to develop efficient organic transformations with the use of alternative electrophiles [ 75 , 76 , 77 , 78 , 79 , 80 , 81 , 82 , 83 , 84 ] under mild reaction conditions, herein we report a hydroxylation of aryl sulfonium salts by using acetohydroxamic acid and oxime as hydroxylative agents, which enabled the efficient assembly of hydroxylated arenes in modest-to-good yields with good functional group compatibility ( Scheme 1 d).…”

Nickel-Catalyzed Direct Cross-Coupling of Aryl Thioether with Aryl Bromide

“…However, the method can mainly be applied to more reactive nitrogen-containing heteroaromatic thioethers derived from benzothiazole, benzoxazole, pyridine, quinoline, pyrimidine, and pyridazine, and no examples were reported for readily available but less reactive aryl thioethers. Thus, as a continued task of our group in developing cross-coupling of two different electrophiles in a straightforward fashion, herein we report a nickel-catalyzed straightforward cross-coupling of aryl thioether with bromoarene in the presence of magnesium and lithium chloride in tetrahydrofuran (THF) at room temperature. The one-pot reactions that preclude the use of organometallics proceeded smoothly through C–S bond cleavage, leading to the corresponding biaryls in moderate to good yields (Scheme c).…”