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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. C−N bond breaking! Alcoholysis of tertiary amide, a C−N bond cleavage reaction, was achieved by a heterogeneous CeO2 catalyst. The present catalytic system has the advantage of being facile and not requiring any additives. The catalyst is moreover recyclable and shows wide substrate scope toward the ester forming process. A possible catalytic mechanism is proposed on the basis of results from density functional theory (DFT) and in situ FT‐IR studies. [ABSTRACT FROM AUTHOR]

The front cover artwork for our 10th Anniversary Issue is provided by the research groups of Ken‐ichi Shimizu at Hokkaido University and Kazunari Yoshizawa at Kyushu University (Japan). The image shows a C−N bond cleavage reaction catalyzed by CeO2. See the Full Paper itself at https://doi.org/10.1002/cctc.201801098. "Experimental and computational investigations indicate that cooperative effects of acid‐base functions of CeO2 are key for the efficient promotion of alcoholysis reactions of tertiary amides through C−N bond cleavage to form esters." This and more about the story behind the research featured on the front cover can be found in this issue's Cover Profile. Read the full text of the corresponding research at https://doi.org/10.1002/cctc.201801098. [ABSTRACT FROM AUTHOR]

The Front Cover shows a C−N bond cleavage reaction catalyzed by CeO2. In their Full Paper, T. Toyao et al. demonstrate that CeO2 promotes catalytic alcoholysis reactions of tertiary amides through C−N bond cleavage to form esters. Unlike typical reactions that use homogeneous catalytic systems and require NHC complexes, the new process is operationally convenient and does not require additives. In addition, the catalyst is recyclable and the process has a wide substrate scope. Both experimental and computational investigations indicate that cooperative effects of acid‐base functions of CeO2 are key for the efficient promotion of the reaction. More information can be found in the Full Paper by T. Toyao et al on page 449 in Issue 1, 2019 (DOI: 10.1002/cctc.201801098). [ABSTRACT FROM AUTHOR]

An abstract of the article "Fe3+exchanged Clay Catalyzed Transamidation of Amides with Amines under Solvent-Free Condition" by S. M. A. Hakim Siddiki, K. Kon and colleagues is presented.

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. C−N bond breaking! Alcoholysis of tertiary amide, a C−N bond cleavage reaction, was achieved by a heterogeneous CeO2 catalyst. The present catalytic system has the advantage of being facile and not requiring any additives. The catalyst is moreover recyclable and shows wide substrate scope toward the ester forming process. A possible catalytic mechanism is proposed on the basis of results from density functional theory (DFT) and in situ FT‐IR studies. [ABSTRACT FROM AUTHOR]

The front cover artwork for our 10th Anniversary Issue is provided by the research groups of Ken‐ichi Shimizu at Hokkaido University and Kazunari Yoshizawa at Kyushu University (Japan). The image shows a C−N bond cleavage reaction catalyzed by CeO2. See the Full Paper itself at https://doi.org/10.1002/cctc.201801098. "Experimental and computational investigations indicate that cooperative effects of acid‐base functions of CeO2 are key for the efficient promotion of alcoholysis reactions of tertiary amides through C−N bond cleavage to form esters." This and more about the story behind the research featured on the front cover can be found in this issue's Cover Profile. Read the full text of the corresponding research at https://doi.org/10.1002/cctc.201801098. [ABSTRACT FROM AUTHOR]