Nickel(II)/N‐Heterocyclic Carbene Catalyzed Desulfinylative Arylation by C−S Cleavage of Aryl Sulfoxides with Phenylboronic Acids

Abstract

Suzuki-Miyaura coupling of haloarenes is the most widely used protocol for the synthesis of biphenyls. Organosulfur compounds are promising electrophiles since they are abundant in nature and versatile in organic synthesis. We report here the desulfinylative Suzuki-Miyaura coupling of aryl sulfoxides with phenylboronic acids using benchstable nickel/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily prepared from common commercial chemicals. The method is applicable to both symmetric and unsymmetric aryl sulfoxides, and a range of biphenyls bearing various functional groups were obtained in up to 94% yield.

Ni-catalyzed C–S bond construction and cleavage

“…86 In 2020, Chen's group employed a Ni/NHC catalytic system to achieve Suzuki-Miyaura type cross-coupling via C-S bond cleavage of diaryl sulfoxides (Scheme 54). 87 A series of biphenyl compounds were afforded by using arylboronic acids as the coupling partners in the current cross-coupling reaction. Both symmetric and unsymmetric aryl sulfoxides were compatible with this transformation.…”

Chromium-catalyzed couplings of C(aryl)–SMe bonds for accessing arylated and alkylated benzaldehyde derivatives

“…[2][3][4] The studies in the field can be traced back to the work by Clayden and Julia using nickel catalysts in the cleavage of C(aryl)-S bonds of aryl sulfones for cross-coupling. 5 Recent advances have included the development of Ni-and Pd-catalyzed couplings using aryl sulfonates, 6 sulfonamides, 7 sulfinate salts 8 and sulfoxides [9][10][11] as partners in the formation of biaryl motifs (Scheme 1a). Rhodium-catalyzed cross-coupling of aryl sulfides with aryl or alkenyl boronic acids has been reported by Weller and Willis.…”