A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid Salts under Mild Conditions

Abstract

The amide derived from 4-hydroxy-l-proline and 2,6-dimethylaniline is a powerful ligand for Cu-catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing the formation of a wide range of (hetero)aryl sulfones from the corresponding (hetero)aryl halides at considerably low catalytic loadings. The coupling of (hetero)aryl iodides and sodium methanesulfinate proceeds at room temperature with only 0.5 mol % CuI and ligand, representing the first example for Cu-catalyzed arylation at both low catalytic loading and room temperature.

Cu-Catalyzed Couplings of Heteroaryl Primary Amines and (Hetero)aryl Bromides with 6-Hydroxypicolinamide Ligands

“…Historically, Cu-catalyzed couplings have been developed using ligands derived from α-amino acids, 1,2-diamines, 1,3-dicarbonyls, and other motifs (Figure ). More recently, Ma’s group has advanced ligand design to the use of oxalamides and amides derived from proline (Figure ). This family of ligands (Figure ) has shown tremendous utility for C–N, C–O, and C–S couplings. , …”

A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides

“…Classical methods for the preparation of sulfones [7] include the oxidation of sulfides, [8] electrophilic aromatic sulfonylation with sulfonyl chlorides, [9] transition metal catalyzed cross coupling of arylsulfinates and aryl halides, [10][11][12] and the insertion of sulfur dioxide. Classical methods for the preparation of sulfones [7] include the oxidation of sulfides, [8] electrophilic aromatic sulfonylation with sulfonyl chlorides, [9] transition metal catalyzed cross coupling of arylsulfinates and aryl halides, [10][11][12] and the insertion of sulfur dioxide.…”

“…Considering their versatile applications, efficient and sustainable methodologies for sulfone synthesis are highly demanded. Classical methods for the preparation of sulfones [7] include the oxidation of sulfides, [8] electrophilic aromatic sulfonylation with sulfonyl chlorides, [9] transition metal catalyzed cross coupling of arylsulfinates and aryl halides, [10][11][12] and the insertion of sulfur dioxide. [13] Recently, the reactions of sulfonyl radicals have received significant consideration in terms of synthetic efficiency and atom economy.…”

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds

“…CuI/DMPHPC (4-hydroxy- l -proline-derived 2,6-dimethyl-aniline amide; 32) is an efficient catalytic system for the coupling of (hetero)aryl halides with sodium sulfinates ( Table 15 ; entry-10 ). 237 Remarkably, low catalyst loadings (0.5 to 5 mol%) and moderate reaction temperatures were used to synthesize a wide range of (hetero)aryl sulfones in good to high yields. As a result, a large number of substituted aryl(hetero) bromides were coupled smoothly with MeSO 2 Na and PhSO 2 Na at 90–100 °C.…”