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Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents

Recently, a variety of 4-substituted Hantzsch esters (XRH) with different structures have been widely researched as alkylation reagents in chemical reactions, and the key step of the chemical process is the elementary step of XRH˙(+) releasing R˙. The purpose of this work is to investigate the essen...

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Autores principales: Shen, Guang-Bin, Xie, Li, Yu, Hao-Yun, Liu, Jie, Fu, Yan-Hua, Yan, Maocai
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9056415/
https://www.ncbi.nlm.nih.gov/pubmed/35520635
http://dx.doi.org/10.1039/d0ra06745h
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author Shen, Guang-Bin
Xie, Li
Yu, Hao-Yun
Liu, Jie
Fu, Yan-Hua
Yan, Maocai
author_facet Shen, Guang-Bin
Xie, Li
Yu, Hao-Yun
Liu, Jie
Fu, Yan-Hua
Yan, Maocai
author_sort Shen, Guang-Bin
collection PubMed
description Recently, a variety of 4-substituted Hantzsch esters (XRH) with different structures have been widely researched as alkylation reagents in chemical reactions, and the key step of the chemical process is the elementary step of XRH˙(+) releasing R˙. The purpose of this work is to investigate the essential factors which determine whether or not an XRH is a great alkylation reagent using density functional theory (DFT). This study shows that the ability of an XRH acting as an alkylation reagent can be reasonably estimated by its ΔG(≠)(RD)(XRH˙(+)) value, which can be conveniently obtained through DFT computations. Moreover, the data also show that ΔG(≠)(RD)(XRH˙(+)) has no simple correlation with the structural features of XRH, including the electronegativity of the R substituent group and the magnitude of steric resistance; therefore, it is difficult to judge whether an XRH can provide R˙ solely by experience. Thus, these results are helpful for chemists to design 4-substituted Hantzsch esters (XRH) with novel structures and to guide the application of XRH as a free radical precursor in organic synthesis.
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spelling pubmed-90564152022-05-04 Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents Shen, Guang-Bin Xie, Li Yu, Hao-Yun Liu, Jie Fu, Yan-Hua Yan, Maocai RSC Adv Chemistry Recently, a variety of 4-substituted Hantzsch esters (XRH) with different structures have been widely researched as alkylation reagents in chemical reactions, and the key step of the chemical process is the elementary step of XRH˙(+) releasing R˙. The purpose of this work is to investigate the essential factors which determine whether or not an XRH is a great alkylation reagent using density functional theory (DFT). This study shows that the ability of an XRH acting as an alkylation reagent can be reasonably estimated by its ΔG(≠)(RD)(XRH˙(+)) value, which can be conveniently obtained through DFT computations. Moreover, the data also show that ΔG(≠)(RD)(XRH˙(+)) has no simple correlation with the structural features of XRH, including the electronegativity of the R substituent group and the magnitude of steric resistance; therefore, it is difficult to judge whether an XRH can provide R˙ solely by experience. Thus, these results are helpful for chemists to design 4-substituted Hantzsch esters (XRH) with novel structures and to guide the application of XRH as a free radical precursor in organic synthesis. The Royal Society of Chemistry 2020-08-25 /pmc/articles/PMC9056415/ /pubmed/35520635 http://dx.doi.org/10.1039/d0ra06745h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Shen, Guang-Bin
Xie, Li
Yu, Hao-Yun
Liu, Jie
Fu, Yan-Hua
Yan, Maocai
Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents
title Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents
title_full Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents
title_fullStr Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents
title_full_unstemmed Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents
title_short Theoretical investigation on the nature of 4-substituted Hantzsch esters as alkylation agents
title_sort theoretical investigation on the nature of 4-substituted hantzsch esters as alkylation agents
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9056415/
https://www.ncbi.nlm.nih.gov/pubmed/35520635
http://dx.doi.org/10.1039/d0ra06745h
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