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Comparison of Cu-ZSM-5 Zeolites and Cu-MOF-505 Metal-Organic Frameworks as Heterogeneous Catalysts for the Mukaiyama Aldol Reaction: A DFT Mechanistic Study

Authors

  • Sudarat Yadnum,

    1. Laboratory for Computational and Applied Chemistry, Department of Chemistry, Faculty of Science and Center of Nanotechnology, Kasetsart University Research and Development Institute, Kasetsart University, Bangkok 10900 (Thailand)
    2. Frontier Research Center, PTT Public Company Limited, 555 Vibhavadi Rangsit Road, Chatuchak, Bangkok 10900 (Thailand)
    3. Center for Advanced Studies in Nanotechnology and its Applications in Chemical, Food, and Agricultural Industries, Kasetsart University ,Bangkok 10900 (Thailand)
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  • Saowapak Choomwattana,

    1. Laboratory for Computational and Applied Chemistry, Department of Chemistry, Faculty of Science and Center of Nanotechnology, Kasetsart University Research and Development Institute, Kasetsart University, Bangkok 10900 (Thailand)
    2. Frontier Research Center, PTT Public Company Limited, 555 Vibhavadi Rangsit Road, Chatuchak, Bangkok 10900 (Thailand)
    3. Center for Advanced Studies in Nanotechnology and its Applications in Chemical, Food, and Agricultural Industries, Kasetsart University ,Bangkok 10900 (Thailand)
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  • Dr. Pipat Khongpracha,

    1. Laboratory for Computational and Applied Chemistry, Department of Chemistry, Faculty of Science and Center of Nanotechnology, Kasetsart University Research and Development Institute, Kasetsart University, Bangkok 10900 (Thailand)
    2. Frontier Research Center, PTT Public Company Limited, 555 Vibhavadi Rangsit Road, Chatuchak, Bangkok 10900 (Thailand)
    3. Center for Advanced Studies in Nanotechnology and its Applications in Chemical, Food, and Agricultural Industries, Kasetsart University ,Bangkok 10900 (Thailand)
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  • Dr. Jakkapan Sirijaraensre,

    1. Laboratory for Computational and Applied Chemistry, Department of Chemistry, Faculty of Science and Center of Nanotechnology, Kasetsart University Research and Development Institute, Kasetsart University, Bangkok 10900 (Thailand)
    2. Frontier Research Center, PTT Public Company Limited, 555 Vibhavadi Rangsit Road, Chatuchak, Bangkok 10900 (Thailand)
    3. Center for Advanced Studies in Nanotechnology and its Applications in Chemical, Food, and Agricultural Industries, Kasetsart University ,Bangkok 10900 (Thailand)
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  • Prof. Dr. Jumras Limtrakul

    Corresponding author
    1. Laboratory for Computational and Applied Chemistry, Department of Chemistry, Faculty of Science and Center of Nanotechnology, Kasetsart University Research and Development Institute, Kasetsart University, Bangkok 10900 (Thailand)
    2. Frontier Research Center, PTT Public Company Limited, 555 Vibhavadi Rangsit Road, Chatuchak, Bangkok 10900 (Thailand)
    3. Center for Advanced Studies in Nanotechnology and its Applications in Chemical, Food, and Agricultural Industries, Kasetsart University ,Bangkok 10900 (Thailand)
    • Laboratory for Computational and Applied Chemistry, Department of Chemistry, Faculty of Science and Center of Nanotechnology, Kasetsart University Research and Development Institute, Kasetsart University, Bangkok 10900 (Thailand)
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Abstract

The density functional theory (DFT) model ONIOM(M06L/6-311++G(2df,2p):UFF was employed to reveal the catalytic activity of CuII in the paddle-wheel unit of the metal-organic framework (MOF)-505 material in the Mukaiyama aldol reaction compared with the activity of Cu-ZSM-5 zeolites. The aldol reaction between a silyl enol ether and formaldehyde catalyzed by the Lewis acidic site of both materials takes place through a concerted pathway, in which the formation of the C[BOND]C bond and the transfer of the silyl group occurs in a single step. MOF-505 and Cu-ZSM-5 are predicted to be efficient catalysts for this reaction as they strongly activate the formaldehyde carbonyl carbon electrophile, which leads to a considerably lower reaction barrier compared with the gas-phase system. Both MOF-505 and Cu-ZSM-5 catalysts stabilize the reacting species along the reaction coordinate, thereby lowering the activation energy, compared to the gas-phase system. The activation barriers for the MOF-505, Cu-ZSM-5, and gas-phase system are 48, 21, and 61 kJ mol−1, respectively. Our results show the importance of the enveloping framework by stabilizing the reacting species and promoting the reaction.

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