Chemoselective Carbon‐Carbon Cross‐Coupling via Palladium‐Catalyzed Copper‐Mediated CS Cleavage of Disulfides

Abstract

An efficient method for carbon-carbon bond formation is described. The process employs the palladium-catalyzed copper-mediated cross-coupling of diheteroaryl disulfides with arylboronic acids or alkynes to deliver C À C coupling products through unreactive C À S bond cleavage. The scope of the coupling reactions, including both the disulfides and arylboronic acids or alkynes, are documented.

The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

“…Diaryl disulfides could also be employed in the Liebeskind–Srogl cross‐coupling reaction. In 2012, the Wang group reported the cross‐coupling reaction between diheteroaryl disulfides 104 and arylboronic acids 2 or terminal alkynes 24 , by employing [Pd(PPh 3 ) 4 ] as a catalyst and CuTC as a mediator (Scheme ) . The presence of a base was also essential in both cases; K 3 PO 4 was the best choice for arylboronic acids, whilst Et 3 N was the best choice for alkyne substrates.…”

C‐O and C‐S coupling reaction of 1,2‐di(pyrimidin‐2‐yl) disulfides with phenols/thiophenols promoted by copper(I) chloride

“…Subsequently, the complex A reacts with phenol producing the intermediate species B , which subsequently undergoes reductive cleavage of the C‐S bond giving the C‐O coupling product 3a . [10b‐f]…”

“…Di(hetero)aryl disulfides are widely used as electrophiles instead of aryl halides for the construction of C‐S bond through S‐S bond cleavage,[8] because that disulfides are structurally symmetrical, air stable, and easy to handle [9]. Recently, we developed a series of method to construct C‐C, C‐N, and C‐S bonds through C‐S and S‐S bonds cleavage of di(hetero)aryl disulfides with various nucleophiles including aryl boronic acids, alkynes, Grignard reagents, and amines [10]. The obtained products tetra‐substituted pyrimidines display wide pharmacological and biological properties[11] In continuation of our work in the formation of the C‐C and C‐Z (Z = O, N, S) bond utilizing 1,2‐di(pyrimidin‐2‐yl) disulfide as an electrophile, we investigated the C‐O and C‐S coupling of the di(hetero)aryl disulfides with phenol and aryl thiol using CuCl to obtain oxylated and sulfenylated pyrimidines (Scheme ).…”

UV‐Light‐Irradiated Trifluoromethylation of Diheteroaryl Disulfides with CF3SO2Na

“…In 2016, the Li group reported a simple and clean strategy for direct trifluoromethylation of arenes/heteroarenes under ultraviolet/visible light irradiation . By taking into consideration of our current interests in the transformation of sulfur‐containing organic compounds, as well as the continued anticipation of new approaches to skeletons of pharmaceutical molecules, we designed a UV light irradiated trifluoromethylation of disulfides with CF 3 SO 2 Na (Scheme d). The conversion has relatively good functional group compatibility, and the disulfide has fully utilized while constructing two S‐CF 3 bonds.…”