Ligand‐Promoted Rh^III‐Catalyzed Thiolation of Benzamides with a Broad Disulfide Scope

Abstract

Al igand-promoted Rh III -catalyzed C(sp 2 ) À Ha ctivation/thiolation of benzamides has been developed. Using bidentate mono-N-protected amino acid ligands led to the first example of Rh III -catalyzed aryl thiolation reactions directed by weakly coordinating directing amide groups.T he reaction tolerates abroad range of amides and disulfide reagents.

Tandem Iridium-Catalyzed Decarbonylative C–H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation

“… 13 Over the past few years the use of C–H activation reactions has emerged as a powerful tool for thioether preparation. 14 Yu and co-workers have reported ligand-promoted Rh(III)-catalyzed aryl thiolation reactions using amide directing groups, 15 and Daugulis presented an aryl sulfenylation of benzoic acid derivatives using bidendate aminoquinoline directing groups. 16 Despite these advances the examples of the arylthiolation of indoles remain extremely limited, with the regiocontrolled C2/C4 methyl thiolation of indoles under Rh-catalyzed conditions using oxime as a directing group by Samatha et al the only example reported.…”

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

“…Rhodium-catalyzed organothiolation reactions of heteroarenes and related compounds using disulfides [ 79 , 80 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 ] and sulfur [ 90 ] have recently been reported. These methods employ stoichiometric or substoichiometric amounts of copper(II) or silver(I) salts.…”

Regioselective 1,2-carbosulfenylation of unactivated alkenesviadirected nickel catalysis

“…In addition, organosul des can be readily transformed into the corresponding sulfoxides and sulfones, which often act as versatile building blocks for organic synthesis. [7][8][9] The synthetic approaches for the e cient construction of C-S bonds include Michael addition, S N 2-type alkylation, cross-coupling, [10][11][12][13] and C-H functionalization [14][15][16] . One powerful and more attractive protocol for their construction is through the carbosulfenylation of alkenes, because this leads to the simultaneous introduction of a carbogenic and a thiol group across a C=C bond to prepare complex, value-added organosulfur products in a single step.…”