A General Copper-Catalyzed Sulfonylation of Arylboronic Acids

Abstract

A general copper-catalyzed method for the sulfonylation of arylboronic acids with sulfinate salts is described. A variety of alkyl-aryl, diaryl, and alkyl-heteroaryl sulfones were synthesized in good yield.

General Copper‐Catalyzed Transformations of Functional Groups from Arylboronic Acids in Water

“…Aryl boron compounds are common chemicals and they are easily prepared from readily available aryl halides (such as aryl bromides and chlorides) and tosylates [14] or by iridium-catalyzed direct borylations of arenes through C À H bond activation. [15] The aryl boron compounds have been used as the starting materials to make aromatic compounds containing various functional groups (including aryl halides, [16] aryl azides, [17] aryl sulfones, [18] phenols, [19] arylamines developed by us [20] and nitroarenes [21] ) through an aerobic oxidative strategy. [22] Unfortunately, the methods need the special ligands of catalysts, organic solvents, and specific temperatures, and the limited substrate scope and unrecyclable catalyst systems greatly limit use of these methods.…”

Cu(I)-Catalysed coupling of Arylsulfinic Salts with Aryl Bromides

“…Sequentially, the appropriate solvent for this reaction was investigated carefully in order to uncover optimum conditions (entries 10-18 using toluene, tetrahydrofuran, dimethoxyethane, acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrolidone and DMI). Importantly, the reaction in aprotic polar solvents leads to higher yields as compared to other solvents (entries [13][14][15][16][17][18] and DMI is the highest yielding solvent.…”

Palladium‐Catalyzed Synthesis of Ammonium Sulfinates from Aryl Halides and a Sulfur Dioxide Surrogate: A Gas‐ and Reductant‐Free Process

“…[25] Accordingly, reaction of 2 g with 2-chlorobenzothiazole provided the corresponding heterocyclic sulfone (7). Treatment of the ammonium sulfinate with sulfuryl chloride resulted in oxidative chlorination and allowed isolation of the derived sulfonyl chloride (8). [26] The moderate yield achieved for this transformation reflects isolation issues.…”

“…Using electrophilic aromatic substitution chemistry limits the accessible molecules to those that conform to the inherent electronic and steric factors which control selectivity in these processes. Alternative procedures exist for both of these functional groups; [8] however, convenient and general methods to access these important molecules are still lacking.…”