Origin of Catalysis by the [Ga4L6]12- Metallocage on the Prins Reaction
Zapirain Gysling, Iker (Universitat Autònoma de Barcelona. Departament de Química)
Gantulga, Norjmaa (Universitat Autònoma de Barcelona. Departament de Química)
Maréchal, Jean-Didier (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)

Date:	2024
Abstract:	The Prins cyclization of citronellal is a significant reaction for synthesizing new carbon-carbon bonds, typically catalyzed by acidic conditions, serving as a crucial industrial intermediate for menthol production. The present work aims to investigate, by means of computational methods, the host-guest catalytic mechanism within the [Ga4L6]12- metallocage, which promotes the formation of minor alkene products, emulating the selectivity observed in biological terpene synthases. A combination of molecular dynamics simulations, DFT, and QM/MM calculations was employed to explore the reaction profiles, revealing the dynamics of encapsulation and the role of protonation and cyclization steps. Our study confirms that the metallocage does not directly modify the reaction but rather provides a unique microenvironment within its cavity that facilitates acid-catalyzed reactions under basic or neutral conditions in solution. Indeed, modification of the basicity of the citronellal reactant once encapsulated turns out to be critical for the process. Moreover, conversely to what is expected, the metallocage does not promote a conformational preorganization of the guest to a more compact conformation prone to undertake the cyclization. Identifying these factors offers a detailed understanding of rate enhancement by metallocages that can be of general applicability.
Grants:	Agencia Estatal de Investigación PID2020-116861GB-I00 Agencia Estatal de Investigación PID2023-150881NB-I00 Ministerio de Ciencia e Innovación PRE2021-098376
Note:	Altres ajuts: acords transformatius de la UAB
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Subject:	Prins reaction ; Supramolecular chemistry ; Metal-organic cages (MOCs) ; Supramolecular catalysis ; Host-guest interactions ; Computational chemistry ; Reaction mechanisms ; Molecular modeling
Published in:	ACS catalysis, Vol. 14, Issue 24 (December 2024) , p. 18722-18733, ISSN 2155-5435

DOI: 10.1021/acscatal.4c04696

12 p, 4.6 MB

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