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MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones

Zr-containing MOF-808 is an excellent heterogeneous catalyst for the diastereoselective Meerwein–Ponndorf–Verley reduction of substituted cyclohexanones. The presence of substituents at the 2 or 3 position of the cyclohexanone ring strongly drives the reaction towards the formation of one of the two...

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Autores principales: Mautschke, Hans Hilmar, Llabrés i Xamena, Francesc X.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9571754/
https://www.ncbi.nlm.nih.gov/pubmed/36234853
http://dx.doi.org/10.3390/molecules27196315
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author Mautschke, Hans Hilmar
Llabrés i Xamena, Francesc X.
author_facet Mautschke, Hans Hilmar
Llabrés i Xamena, Francesc X.
author_sort Mautschke, Hans Hilmar
collection PubMed
description Zr-containing MOF-808 is an excellent heterogeneous catalyst for the diastereoselective Meerwein–Ponndorf–Verley reduction of substituted cyclohexanones. The presence of substituents at the 2 or 3 position of the cyclohexanone ring strongly drives the reaction towards the formation of one of the two possible isomers. For 3-methyl cyclohexanone, the available space inside the MOF pores allows the formation of the bulkier transition state leading to the thermodynamically stable 3-cis-cyclohexanol. For 2-methyl cyclohexanone, the reaction rate is much slower and the final diastereoselectivity depends on the size of the alcohol used. Finally, reduction of 2-phenyl cyclohexanone is considerable faster over MOF-808 than for any other catalyst reported so far. The large size of the phenyl favors the selective formation (up to 94% selectivity) of the cis-alcohol, which goes through a less hindered transition state.
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spelling pubmed-95717542022-10-17 MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones Mautschke, Hans Hilmar Llabrés i Xamena, Francesc X. Molecules Article Zr-containing MOF-808 is an excellent heterogeneous catalyst for the diastereoselective Meerwein–Ponndorf–Verley reduction of substituted cyclohexanones. The presence of substituents at the 2 or 3 position of the cyclohexanone ring strongly drives the reaction towards the formation of one of the two possible isomers. For 3-methyl cyclohexanone, the available space inside the MOF pores allows the formation of the bulkier transition state leading to the thermodynamically stable 3-cis-cyclohexanol. For 2-methyl cyclohexanone, the reaction rate is much slower and the final diastereoselectivity depends on the size of the alcohol used. Finally, reduction of 2-phenyl cyclohexanone is considerable faster over MOF-808 than for any other catalyst reported so far. The large size of the phenyl favors the selective formation (up to 94% selectivity) of the cis-alcohol, which goes through a less hindered transition state. MDPI 2022-09-25 /pmc/articles/PMC9571754/ /pubmed/36234853 http://dx.doi.org/10.3390/molecules27196315 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Mautschke, Hans Hilmar
Llabrés i Xamena, Francesc X.
MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones
title MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones
title_full MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones
title_fullStr MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones
title_full_unstemmed MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones
title_short MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones
title_sort mof-808 as a highly active catalyst for the diastereoselective reduction of substituted cyclohexanones
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9571754/
https://www.ncbi.nlm.nih.gov/pubmed/36234853
http://dx.doi.org/10.3390/molecules27196315
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