Efficient N-Heterocyclic Carbene/Ruthenium Catalytic Systems for the Alcohol Amidation with Amines

Involvement of Poly-Carbene Complexes?

Hua Cheng, Mao Qian Xiong, Ni Zhang, Hua Jing Wang, Yang Miao, Wei Su, Ye Yuan, Cheng Chen, Francis Verpoort

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The atom-economic direct amidation of alcohols with amines has been recently highlighted as an attractive and promising transformation. Among the versatile reported catalytic systems, in situ generated N-heterocyclic carbene (NHC)/ruthenium (Ru) catalytic systems have demonstrated their advantages such as easy operation and use of commercial Ru compounds. However, the existing catalyst loadings are relatively high, and additional insights for the in situ catalyst generation are still not well-documented. In this work, a variety of benzimidazole-based NHC precursors were initially synthesized. Through the screening of various NHC precursors and other reaction conditions, active in situ catalytic systems were discovered for the efficient amide synthesis. Notably, the catalyst loading is as low as 0.5 mol %. Furthermore, additional experiments were performed to validate the rationale for the superiority of the current catalytic systems over our previous system. It was observed that the ligand structure is one of the reasons for the higher activity. In addition, the higher ratio of the NHC precursor/[Ru] is another important factor for the improvement. Further HR-MS analysis identified the formation of two mono-NHC-Ru species as major species and two Ru species bearing multiple NHC ligands as minor species. Hopefully, the efficient and readily-accessible catalytic systems reported herein could demonstrate great potential for further practical applications.

Original languageEnglish
Pages (from-to)4338-4345
Number of pages8
JournalChemCatChem
Volume10
Issue number19
DOIs
Publication statusPublished - 9 Oct 2018

Fingerprint

Ruthenium
carbenes
ruthenium
Amines
amines
alcohols
Alcohols
Catalysts
Ruthenium compounds
Bearings (structural)
Ligands
catalysts
Ruthenium Compounds
ruthenium compounds
Amides
Screening
ligands
Atoms
amides
Economics

Keywords

  • amide synthesis
  • atom-economic
  • In situ
  • N-heterocyclic carbene (s)
  • ruthenium

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Efficient N-Heterocyclic Carbene/Ruthenium Catalytic Systems for the Alcohol Amidation with Amines : Involvement of Poly-Carbene Complexes? / Cheng, Hua; Xiong, Mao Qian; Zhang, Ni; Wang, Hua Jing; Miao, Yang; Su, Wei; Yuan, Ye; Chen, Cheng; Verpoort, Francis.

In: ChemCatChem, Vol. 10, No. 19, 09.10.2018, p. 4338-4345.

Research output: Contribution to journalArticle

Cheng, Hua ; Xiong, Mao Qian ; Zhang, Ni ; Wang, Hua Jing ; Miao, Yang ; Su, Wei ; Yuan, Ye ; Chen, Cheng ; Verpoort, Francis. / Efficient N-Heterocyclic Carbene/Ruthenium Catalytic Systems for the Alcohol Amidation with Amines : Involvement of Poly-Carbene Complexes?. In: ChemCatChem. 2018 ; Vol. 10, No. 19. pp. 4338-4345.
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