New class of RSO<sub>2</sub>-NHC ligands and Pd/RSO<sub>2</sub>-NHC complexes with tailored electronic properties and high performance in catalytic C–C and C–N bonds formation

Pasyukov, Dmitry V.; Шевченко, М. А.; Aстахов, А. В.; Minyaev, Mikhail E.; Zhang, Yu; Чернышев, В. М.; Ananikov, Valentine P.

doi:10.1039/d3dt02296j

Cited by 10 publications

References 98 publications

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4‐Halomethyl‐Substituted Imidazolium Salts: A Versatile Platform for the Synthesis of Functionalized NHC Precursors

Pasyukov,

Shevchenko,

Minyaev

et al. 2024

Chemistry An Asian Journal

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N,Nʹ‐Diarylimidazolium salts containing haloalkyl functional groups that are reactive with various nucleophiles are considered to be promising reagents for the preparation of functionalized N‐heterocyclic carbene (NHC) ligands, which are in demand in catalysis, materials science, and biomedical research. Recently, 4‐chloromethyl‐functionalized N,N'‐diarylimidazolium salts became readily available via the condensation of N,N'‐diaryl‐2‐methyl‐1,4‐diaza‐1,3‐butadienes with ethyl orthoformate and Me3SiCl, but these compounds were found to have insufficient reactivity in reactions with many nucleophiles. These chloromethyl salts were studied as precursors in the synthesis of bromo‐ and iodomethyl‐functionalized imidazolium salts by halide anion exchange. The 4‐ICH2‐functionalized products were found to be unstable, whereas a series of novel 4‐bromomethyl functionalized N,N'‐diarylimidazolium salts were obtained in good yields. These bromomethyl‐functionalized imidazolium salts were found to be significantly more reactive towards various N, O and S nucleophiles than the chloromethyl counterparts and enabled the preparation of previously inaccessible heteroatom‐functionalized imidazolium salts, some of which were successfully used as NHC proligands in the preparation of Pd/NHC and Au/NHC complexes.

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4‐Halomethyl‐Substituted Imidazolium Salts: A Versatile Platform for the Synthesis of Functionalized NHC Precursors

Pasyukov,

Shevchenko,

Minyaev

et al. 2024

Chemistry An Asian Journal

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Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

Chernenko,

Baydikova,

Kutyrev

et al. 2024

ChemCatChem

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Aryl chlorides, due to their affordability and accessibility, are preferred reagents in Pd‐catalyzed arylation reactions. However, the reactivity of aryl chlorides is often reduced compared to aryl bromides and iodides due to the significantly higher barriers of the oxidative addition stage. This research introduces a novel design for NHC ligands, which notably enhances the efficiency of Pd/NHC catalytic systems in reactions where oxidative addition of aryl chloride is the rate‐limiting step. This design leverages a synergy between specific steric characteristics and the anionic nature of the newly fashioned 1,2,4‐triazol‐5‐ylidene ligands. These ligands, inspired by Nitron‐type designs, can be ionized under basic conditions due to their NH‐acidic aryl(alkyl)amino groups. Detailed experimental and DFT studies revealed that the deprotonation of these NHCs promotes electron donation to the metal center, promoting the oxidative addition of aryl chloride. The specially optimized ATPr ligand, featuring 2,6‐diisopropylphenyl groups, displayed remarkable catalytic efficacy in the Suzuki‐Miyaura reaction and improved outcomes in ketone α‐arylation and Buchwald‐Hartwig reactions with unactivated aryl chlorides. The insights and strategies established in this study provide rational considerations for further advancements in NHC designs and their applications in metal‐catalyzed reactions.

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77Se NMR spectroscopy of selenium adducts of N-heterocyclic carbenes

Kahnert,

Pruschinski,

Schmidt

2024

Advances in Heterocyclic Chemistry

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New class of RSO₂-NHC ligands and Pd/RSO₂-NHC complexes with tailored electronic properties and high performance in catalytic C–C and C–N bonds formation

Abstract: Imidazolium salts have received ubiquitous applications as N-heterocyclic carbene precursors and metal nanoparticle stabilizers in catalysis and metallodrug research. Substituents directly attached to the imidazole ring can have a significant...

Cited by 10 publications

References 98 publications

4‐Halomethyl‐Substituted Imidazolium Salts: A Versatile Platform for the Synthesis of Functionalized NHC Precursors

4‐Halomethyl‐Substituted Imidazolium Salts: A Versatile Platform for the Synthesis of Functionalized NHC Precursors

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

77Se NMR spectroscopy of selenium adducts of N-heterocyclic carbenes

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New class of RSO2-NHC ligands and Pd/RSO2-NHC complexes with tailored electronic properties and high performance in catalytic C–C and C–N bonds formation

Abstract: Imidazolium salts have received ubiquitous applications as N-heterocyclic carbene precursors and metal nanoparticle stabilizers in catalysis and metallodrug research. Substituents directly attached to the imidazole ring can have a significant...

Cited by 10 publications

References 98 publications

4‐Halomethyl‐Substituted Imidazolium Salts: A Versatile Platform for the Synthesis of Functionalized NHC Precursors

4‐Halomethyl‐Substituted Imidazolium Salts: A Versatile Platform for the Synthesis of Functionalized NHC Precursors

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

77Se NMR spectroscopy of selenium adducts of N-heterocyclic carbenes

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New class of RSO₂-NHC ligands and Pd/RSO₂-NHC complexes with tailored electronic properties and high performance in catalytic C–C and C–N bonds formation