Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO2

Takashi Toyao, Md Nurnobi Rashed, Yoshitsugu Morita, Takashi Kamachi, S. M.A. Hakim Siddiki, Md A. Ali, A. S. Touchy, Kenichi Kon, Zen Maeno, Kazunari Yoshizawa, Ken ichi Shimizu

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

CeO2 has been found to promote ester forming alcoholysis reactions of tertiary amides. The present catalytic system is operationally simple, recyclable, and it does not require additives. The esterification process displays a wide substrate scope (>45 examples; up to 93 % isolated yield). Results of a density functional theory (DFT) study combined with in situ FT-IR observations indicate that the process proceeds through rate limiting addition of a CeO2 lattice oxygen to the carbonyl group of the adsorbed acetamide species with energy barrier of 17.0 kcal/mol. This value matches well with experimental value (17.9 kcal/mol) obtained from analysis of the Arrhenius plot. Further studies by in situ FT-IR and temperature programmed desorption using probe molecules demonstrate that both acidic and basic properties are important, and consequently, CeO2 showed the best performance for the C−N bond cleavage reaction.

Original languageEnglish
Pages (from-to)449-456
Number of pages8
JournalChemCatChem
Volume11
Issue number1
DOIs
Publication statusPublished - Jan 9 2019

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Arrhenius plots
Energy barriers
Esterification
Temperature programmed desorption
Amides
amides
Density functional theory
cleavage
Esters
alcohols
Alcohols
Oxygen
Molecules
Substrates
esters
plots
desorption
density functional theory
probes
oxygen

All Science Journal Classification (ASJC) codes

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

Cite this

Toyao, T., Nurnobi Rashed, M., Morita, Y., Kamachi, T., Hakim Siddiki, S. M. A., Ali, M. A., ... Shimizu, K. I. (2019). Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO2 ChemCatChem, 11(1), 449-456. https://doi.org/10.1002/cctc.201801098

Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO2 . / Toyao, Takashi; Nurnobi Rashed, Md; Morita, Yoshitsugu; Kamachi, Takashi; Hakim Siddiki, S. M.A.; Ali, Md A.; Touchy, A. S.; Kon, Kenichi; Maeno, Zen; Yoshizawa, Kazunari; Shimizu, Ken ichi.

In: ChemCatChem, Vol. 11, No. 1, 09.01.2019, p. 449-456.

Research output: Contribution to journalArticle

Toyao, T, Nurnobi Rashed, M, Morita, Y, Kamachi, T, Hakim Siddiki, SMA, Ali, MA, Touchy, AS, Kon, K, Maeno, Z, Yoshizawa, K & Shimizu, KI 2019, 'Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO2 ', ChemCatChem, vol. 11, no. 1, pp. 449-456. https://doi.org/10.1002/cctc.201801098
Toyao T, Nurnobi Rashed M, Morita Y, Kamachi T, Hakim Siddiki SMA, Ali MA et al. Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO2 ChemCatChem. 2019 Jan 9;11(1):449-456. https://doi.org/10.1002/cctc.201801098
Toyao, Takashi ; Nurnobi Rashed, Md ; Morita, Yoshitsugu ; Kamachi, Takashi ; Hakim Siddiki, S. M.A. ; Ali, Md A. ; Touchy, A. S. ; Kon, Kenichi ; Maeno, Zen ; Yoshizawa, Kazunari ; Shimizu, Ken ichi. / Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO2 In: ChemCatChem. 2019 ; Vol. 11, No. 1. pp. 449-456.
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