(NHC-olefin)-nickel(0) nanoparticles as catalysts for the (<i>Z</i>)-selective semi-hydrogenation of alkynes and ynamides

Avello, Marta; Golling, Stéphane; Truong‐Phuoc, Lai; Vidal, Loı̈c; Romero, Thierry; Papaefthymiou, Vasiliki; Gruber, Nathalie; Chetcuti, Michael J.; Leroux, Frédéric R.; Donnard, Morgan; Ritleng, Vincent; Pham‐Huu, Cuong; Michon, Christophe

doi:10.1039/d2cc05302k

Cited by 9 publications

(5 citation statements)

References 45 publications

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“…The employment of TfOH (1.5 equiv) and water additive (15 equiv), heating at 60 °C in p -xylene for 6 h were currently the most proper conditions, and provided the optimal yield of 3a as 82%. The Z -selectivity in product 3a , unlike conventional alkenes, could be ascribed to the intramolecular hydrogen bonding effect between the NH group and the oxygen. …”

Section: Resultsmentioning

confidence: 96%

Unlock the C–N Bond Amidation of Enaminones: Metal-Free Synthesis of Enamides by Water-Assisted Transamidation

Wu,

Chen,

Liu

et al. 2023

J. Org. Chem.

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The C−N bond transamidation of primary amides with N,N-dimethyl enaminones has been efficiently realized by heating in the presence of trifluoromethanesulfonic acid (TfOH). The method enables the practical synthesis of valuable enamides without the use of any metal reagent. In addition, this transamidation protocol can also be expanded to the reactions of sulfonamides, and the late-stage functionalization on sulfonamide drugs such as Celecoxib and Valdecoxib has been verified. Moreover, the participation of water in assisting the transamidation process has been identified by the isotope labeling experiments using D 2 O, disclosing a new possibility in designing catalytic tactic to other transamidation reactions.

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Section: Resultsmentioning

confidence: 96%

Unlock the C–N Bond Amidation of Enaminones: Metal-Free Synthesis of Enamides by Water-Assisted Transamidation

Wu,

Chen,

Liu

et al. 2023

J. Org. Chem.

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“…Methods for the synthesis of terminal E -configured alkenyl nitriles, including Fe-catalyzed deoxynitrogenation of carboxylic acids, , Ni or Rh-mediated hydrocyanation across carbon–carbon multiple bond, , and Fe-catalyzed direct functionalization of aryl ethenes, have been established. However, many of these methods require environmentally benign transition-metal catalysts.…”

Section: Resultsmentioning

confidence: 99%

Exploring Efficient Dual-Phase Emissive Fluorophores with High Mobility by Integrating a Rigid Donor and Flexible Acceptor

Guo,

Jin,

Zhang

et al. 2024

ACS Appl. Mater. Interfaces

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Developing luminogens with a high emission efficiency in both singlemolecule and aggregate states, as well as high mobility, shows promise for advancing the iteration and update of organic optoelectronic materials. However, achieving a delicate balance between the plane configuration of luminophores and the strong exciton interactions of aggregates is a formidable task from the molecular design perspective. This dilemma was overcome by integrating a rigid donor and flexible acceptor to establish donor−acceptor (D−A) type emitters. The π-conjugate-extended donor ensures the substantial planarity of these molecules, allowing strong emission in solution with photoluminescence quantum yield values of 86% and 75%. Furthermore, the restricted molecular motion of the aggregation-induced emission moiety and the formation of J-aggregates reduce the quenching effect, leading to a high emissive efficiency of 85% and 91% in the aggregate state. The mildly distorted D−A geometry builds moderate electrostatic interaction, resulting in high mobility with μ M,h of 7.12 × 10 −5 and 3.27 × 10 −4 cm 2 /V s. Additionally, an improved synthesized procedure for terminal E-configured acrylonitrile with metal-free and concise reaction conditions is presented. The successful application of the synthesized compounds in organic light-emitting diode devices demonstrates the practicability of the molecular design strategy with connecting a rigid donor and flexible acceptor.

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“…Recently, Ritleng, Pham-Huu, Michon, and co-workers reported a ( Z )-selective semihydrogenation of alkynes and ynamides using NHC ( N -heterocyclic carbene)-supported Ni(0) nanoparticles (NPs) (Scheme ). Ni(0) NPs are viewed as particularly effective catalysts due to their high surface area, but agglomeration often limits their catalytic activity, a phenomenon also observed in the process development of heterogeneous reactions. Although previous methods demonstrated NHC stabilization and minimal loss of activity, the use of the NHC–olefin complex offers a strong σ-donor and a π-coordinating moiety that further prevents aggregation.…”

Section: Ni Catalysismentioning

confidence: 99%

Recent Advances in Nonprecious Metal Catalysis

Bernhardson,

Hansen,

Hubbell

et al. 2023

Org. Process Res. Dev.

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(NHC-olefin)-nickel(0) nanoparticles as catalysts for the (Z)-selective semi-hydrogenation of alkynes and ynamides

Abstract: Nickel(0) nanoparticles coordinated to NHC ligands bearing a N-coordinated cynnamyl moiety were readily prepared by reduction of a [NiCpBr(NHC-cynnamyl)] complex with methyl magnesium bromide. The combination of a strong sigma-donor...

Cited by 9 publications

References 45 publications

Unlock the C–N Bond Amidation of Enaminones: Metal-Free Synthesis of Enamides by Water-Assisted Transamidation

Unlock the C–N Bond Amidation of Enaminones: Metal-Free Synthesis of Enamides by Water-Assisted Transamidation

Exploring Efficient Dual-Phase Emissive Fluorophores with High Mobility by Integrating a Rigid Donor and Flexible Acceptor

Recent Advances in Nonprecious Metal Catalysis

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