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Synthesis of carbene-metal-amido (CMA) complexes and their use as precatalysts for the activator-free, gold-catalyzed addition of carboxylic acids to alkynes

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Abstract
A straightforward synthetic protocol leading to carbene-metal-amido (CMA) complexes (metal=Au, Cu) using a mild base and an environmentally desirable solvent (EtOH) has been explored, with a focus on complexes bearing backbone-substituted N-heterocyclic carbene (NHC) ligands, including BIAN-NHCs (BIAN=bis(imino)acenaphthene). The novel CMAs were structurally characterized, and gold-based CMAs bearing diverse NHCs were screened as simple, Bronsted-basic precatalysts. The readily accessible complexes display high catalytic activity in the intermolecular and intramolecular hydrocarboxylation of internal alkynes and alkynoic acids respectively, while the screening reveals the ancillary ligand effect of NHCs in these catalytic systems.
Keywords
INTERNAL ALKYNES, GOLD(I)-CATALYZED ADDITION, LIGANDS SYNTHESIS, ACETYLENIC ACIDS, SILVER-FREE, EFFICIENT, CYCLOISOMERIZATION, REACTIVITY, COPPER, HYDROCARBOXYLATION, alkynes, BIAN-NHC, carbene-metal-amido, carboxylic acids, gold, N-heterocyclic carbene complexes

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Citation

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MLA
ishfaq, Ibni Hashim, et al. “Synthesis of Carbene-Metal-Amido (CMA) Complexes and Their Use as Precatalysts for the Activator-Free, Gold-Catalyzed Addition of Carboxylic Acids to Alkynes.” CHEMISTRY-A EUROPEAN JOURNAL, vol. 28, no. 47, 2022, doi:10.1002/chem.202201224.
APA
ishfaq, I. H., Tzouras, N., Janssens, W., Scattolin, T., Bourda, L., Bhandary, S., … Cazin, C. (2022). Synthesis of carbene-metal-amido (CMA) complexes and their use as precatalysts for the activator-free, gold-catalyzed addition of carboxylic acids to alkynes. CHEMISTRY-A EUROPEAN JOURNAL, 28(47). https://doi.org/10.1002/chem.202201224
Chicago author-date
ishfaq, Ibni Hashim, Nikolaos Tzouras, Wim Janssens, Thomas Scattolin, Laurens Bourda, Subhrajyoti Bhandary, Kristof Van Hecke, Steven Nolan, and Catherine Cazin. 2022. “Synthesis of Carbene-Metal-Amido (CMA) Complexes and Their Use as Precatalysts for the Activator-Free, Gold-Catalyzed Addition of Carboxylic Acids to Alkynes.” CHEMISTRY-A EUROPEAN JOURNAL 28 (47). https://doi.org/10.1002/chem.202201224.
Chicago author-date (all authors)
ishfaq, Ibni Hashim, Nikolaos Tzouras, Wim Janssens, Thomas Scattolin, Laurens Bourda, Subhrajyoti Bhandary, Kristof Van Hecke, Steven Nolan, and Catherine Cazin. 2022. “Synthesis of Carbene-Metal-Amido (CMA) Complexes and Their Use as Precatalysts for the Activator-Free, Gold-Catalyzed Addition of Carboxylic Acids to Alkynes.” CHEMISTRY-A EUROPEAN JOURNAL 28 (47). doi:10.1002/chem.202201224.
Vancouver
1.
ishfaq IH, Tzouras N, Janssens W, Scattolin T, Bourda L, Bhandary S, et al. Synthesis of carbene-metal-amido (CMA) complexes and their use as precatalysts for the activator-free, gold-catalyzed addition of carboxylic acids to alkynes. CHEMISTRY-A EUROPEAN JOURNAL. 2022;28(47).
IEEE
[1]
I. H. ishfaq et al., “Synthesis of carbene-metal-amido (CMA) complexes and their use as precatalysts for the activator-free, gold-catalyzed addition of carboxylic acids to alkynes,” CHEMISTRY-A EUROPEAN JOURNAL, vol. 28, no. 47, 2022.
@article{01GT923MWDRADHWD9B8AWSPADC,
  abstract     = {{A straightforward synthetic protocol leading to carbene-metal-amido (CMA) complexes (metal=Au, Cu) using a mild base and an environmentally desirable solvent (EtOH) has been explored, with a focus on complexes bearing backbone-substituted N-heterocyclic carbene (NHC) ligands, including BIAN-NHCs (BIAN=bis(imino)acenaphthene). The novel CMAs were structurally characterized, and gold-based CMAs bearing diverse NHCs were screened as simple, Bronsted-basic precatalysts. The readily accessible complexes display high catalytic activity in the intermolecular and intramolecular hydrocarboxylation of internal alkynes and alkynoic acids respectively, while the screening reveals the ancillary ligand effect of NHCs in these catalytic systems.}},
  articleno    = {{e202201224}},
  author       = {{ishfaq, Ibni Hashim and Tzouras, Nikolaos and Janssens, Wim and Scattolin, Thomas and Bourda, Laurens and Bhandary, Subhrajyoti and Van Hecke, Kristof and Nolan, Steven and Cazin, Catherine}},
  issn         = {{0947-6539}},
  journal      = {{CHEMISTRY-A EUROPEAN JOURNAL}},
  keywords     = {{INTERNAL ALKYNES,GOLD(I)-CATALYZED ADDITION,LIGANDS SYNTHESIS,ACETYLENIC ACIDS,SILVER-FREE,EFFICIENT,CYCLOISOMERIZATION,REACTIVITY,COPPER,HYDROCARBOXYLATION,alkynes,BIAN-NHC,carbene-metal-amido,carboxylic acids,gold,N-heterocyclic carbene complexes}},
  language     = {{eng}},
  number       = {{47}},
  pages        = {{7}},
  title        = {{Synthesis of carbene-metal-amido (CMA) complexes and their use as precatalysts for the activator-free, gold-catalyzed addition of carboxylic acids to alkynes}},
  url          = {{http://doi.org/10.1002/chem.202201224}},
  volume       = {{28}},
  year         = {{2022}},
}

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