Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes

Abstract

The performance of a set of mono- and bimetallic Rh(i) and Ir(i) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkynes.

Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges

“…A sequential alkyne dimerization–hydrothiolation tandem reaction was also successfully carried out . Cationic and neutral rhodium complexes with N - donor-functionalized 1,2,3-triazol-5-ylidene ligands were studied for application in catalysis, and a neutral dicarbonyl complex was shown to be selective for hydrothiolation of an alkyne with an aryl thiol. , …”

“…924 Cationic and neutral rhodium complexes with N-donor-functionalized 1,2,3-triazol-5-ylidene ligands were studied for application in catalysis, and a neutral dicarbonyl complex was shown to be selective for hydrothiolation of an alkyne with an aryl thiol. 925,926 Rh-mediated transformations were utilized for the design of catalytic systems for materials science applications. Ogawa and co-workers succeeded in the synthesis of sulfur-containing πconjugated polymers.…”

“…926 The authors have reported that the studied Rh(I) complexes outperformed the similar Ir(I) complexes in terms of activity and selectivity. 926 However, Ir complexes can be synthetically very important when photoredox conditions are applied. Glorius and coworkers have developed an Ir photoredox catalytic system for carrying out hydrothiolation of alkenes (Scheme 292).…”

Recent Metal-Catalyzed Methods for Thioether Synthesis

“…169 Examples of branched selectivity have been demonstrated using an acid-base metal-ligand cooperative catalysis enabled by specific design of 1,2,3-triazol-5-ydinen ligand. 170 The same group also utilized dinuclear complexes for the same transformation 171 and also developed a sequential approach for dimerization/hydrothiolation of alkynes to yield products with multiple unsaturated functional groups. 172 In terms of other sp-hybridized starting materials, Pritzius and Breit developed a methodology based on enantioselective hydrothiolation of allenes 73 furnishing the valuable branched allylic sulfides 74 (Scheme 46).…”

Cs2CO3-Promoted Hydrothiolation of Alkynes with Aryl Thioureas: Stereoselective Synthesis of (Z)-Vinyl Sulfides

“…In recent years, the development of metal-catalyzed alkyne hydrothiolation has improved the regioselectivity and stereoselectivity. Copper, palladium, nickel, rhodium, indium, ruthenium, and gold complexes have been successfully used as catalysts for the alkyne hydrothiolations, which generally give the predominant E -isomers.…”