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Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study

Biomass-derived γ-valerolactone (GVL) is a versatile chemical that can be used in various fields. As an efficient, cheap, and sustainable catalyst, Al(OiPr)(3) has been successfully used in the conversion of methyl levulinate (ML) to GVL in the solvent isopropanol (IPA). However, the molecular mecha...

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Autores principales: Ju, Zhaoyang, Feng, Shaokeng, Ren, Lanhui, Lei, Tingyu, Cheng, Haixiang, Yu, Mengting, Ge, Chengsheng
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8979184/
https://www.ncbi.nlm.nih.gov/pubmed/35425337
http://dx.doi.org/10.1039/d1ra08429a
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author Ju, Zhaoyang
Feng, Shaokeng
Ren, Lanhui
Lei, Tingyu
Cheng, Haixiang
Yu, Mengting
Ge, Chengsheng
author_facet Ju, Zhaoyang
Feng, Shaokeng
Ren, Lanhui
Lei, Tingyu
Cheng, Haixiang
Yu, Mengting
Ge, Chengsheng
author_sort Ju, Zhaoyang
collection PubMed
description Biomass-derived γ-valerolactone (GVL) is a versatile chemical that can be used in various fields. As an efficient, cheap, and sustainable catalyst, Al(OiPr)(3) has been successfully used in the conversion of methyl levulinate (ML) to GVL in the solvent isopropanol (IPA). However, the molecular mechanism of this conversion catalyzed by Al(OiPr)(3) remains ambiguous. To investigate the mechanism of the conversion of ML to GVL catalyzed by Al(OiPr)(3), the reaction pathways, including the transesterification, Meerwein–Ponndorf–Verley (MPV) hydrogenation, and ring-closure steps, were probed using density functional theory (DFT) calculations at the M062X-D3/def2-TZVP level. Among the elementary steps, it is found that ring-closure is the rate-determining step and that Al(3+) can coordinate with the oxygen of 2-hydroxy-isopropyl levulinate (2HIPL) to catalyze the last ring-closure step. A four-centered transition state can be formed, and Al(OiPr)(3) shows a strong catalytic effect in the two steps of the ester exchange reaction. The center of Al(OiPr)(3) mainly coordinates with the carbonyl oxygen atom of the ester to catalyze the reaction. The present study provides some help in understanding the conversion mechanism of ML to GVL and designing more effective catalysts for use in biomass conversion chemistry.
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spelling pubmed-89791842022-04-13 Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study Ju, Zhaoyang Feng, Shaokeng Ren, Lanhui Lei, Tingyu Cheng, Haixiang Yu, Mengting Ge, Chengsheng RSC Adv Chemistry Biomass-derived γ-valerolactone (GVL) is a versatile chemical that can be used in various fields. As an efficient, cheap, and sustainable catalyst, Al(OiPr)(3) has been successfully used in the conversion of methyl levulinate (ML) to GVL in the solvent isopropanol (IPA). However, the molecular mechanism of this conversion catalyzed by Al(OiPr)(3) remains ambiguous. To investigate the mechanism of the conversion of ML to GVL catalyzed by Al(OiPr)(3), the reaction pathways, including the transesterification, Meerwein–Ponndorf–Verley (MPV) hydrogenation, and ring-closure steps, were probed using density functional theory (DFT) calculations at the M062X-D3/def2-TZVP level. Among the elementary steps, it is found that ring-closure is the rate-determining step and that Al(3+) can coordinate with the oxygen of 2-hydroxy-isopropyl levulinate (2HIPL) to catalyze the last ring-closure step. A four-centered transition state can be formed, and Al(OiPr)(3) shows a strong catalytic effect in the two steps of the ester exchange reaction. The center of Al(OiPr)(3) mainly coordinates with the carbonyl oxygen atom of the ester to catalyze the reaction. The present study provides some help in understanding the conversion mechanism of ML to GVL and designing more effective catalysts for use in biomass conversion chemistry. The Royal Society of Chemistry 2022-01-19 /pmc/articles/PMC8979184/ /pubmed/35425337 http://dx.doi.org/10.1039/d1ra08429a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Ju, Zhaoyang
Feng, Shaokeng
Ren, Lanhui
Lei, Tingyu
Cheng, Haixiang
Yu, Mengting
Ge, Chengsheng
Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study
title Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study
title_full Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study
title_fullStr Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study
title_full_unstemmed Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study
title_short Probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by Al(OiPr)(3) in an alcohol solvent: a DFT study
title_sort probing the mechanism of the conversion of methyl levulinate into γ-valerolactone catalyzed by al(oipr)(3) in an alcohol solvent: a dft study
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8979184/
https://www.ncbi.nlm.nih.gov/pubmed/35425337
http://dx.doi.org/10.1039/d1ra08429a
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