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Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study
It is very important to develop multiple C–H substitution reactions of simple alkenes to obtain complex unsaturated components. The present study focuses on a theoretical investigation of the plausible mechanism in the Fe(OTf)(3)-catalyzed tandem amidomethylative reactions of α-phenylstyrene. Bis(to...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9284522/ https://www.ncbi.nlm.nih.gov/pubmed/35919169 http://dx.doi.org/10.1039/d2ra02727e |
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author | Cheng, Yaxuan Yang, Siwei Zhao, Chaoyu Liu, Huiling |
author_facet | Cheng, Yaxuan Yang, Siwei Zhao, Chaoyu Liu, Huiling |
author_sort | Cheng, Yaxuan |
collection | PubMed |
description | It is very important to develop multiple C–H substitution reactions of simple alkenes to obtain complex unsaturated components. The present study focuses on a theoretical investigation of the plausible mechanism in the Fe(OTf)(3)-catalyzed tandem amidomethylative reactions of α-phenylstyrene. Bis(tosylamido)methane is activated by Fe(OTf)(3) to form tosylformaldimine and its Fe(OTf)(3)-adduct. The Fe(OTf)(3)-adduct undergoes an intermolecular aza-Prins reaction with α-phenylstyrene to form allylamide. The DFT data support the formation of the hexahydropyrimidine derivative from allylamide, and “condensation/iminium homologation/intramolecular aza-Prins” is the optimal reaction path. At the same time, a possible reaction pathway for the conversion of the hydrolysate 1,3-diamide derivative to the hexahydropyrimidine (HHP) derivative is given. This work is thus instructive for understanding Fe(iii)-based tandem catalysis for the amidomethylative multiple-substitution reactions of alkenes. |
format | Online Article Text |
id | pubmed-9284522 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-92845222022-08-01 Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study Cheng, Yaxuan Yang, Siwei Zhao, Chaoyu Liu, Huiling RSC Adv Chemistry It is very important to develop multiple C–H substitution reactions of simple alkenes to obtain complex unsaturated components. The present study focuses on a theoretical investigation of the plausible mechanism in the Fe(OTf)(3)-catalyzed tandem amidomethylative reactions of α-phenylstyrene. Bis(tosylamido)methane is activated by Fe(OTf)(3) to form tosylformaldimine and its Fe(OTf)(3)-adduct. The Fe(OTf)(3)-adduct undergoes an intermolecular aza-Prins reaction with α-phenylstyrene to form allylamide. The DFT data support the formation of the hexahydropyrimidine derivative from allylamide, and “condensation/iminium homologation/intramolecular aza-Prins” is the optimal reaction path. At the same time, a possible reaction pathway for the conversion of the hydrolysate 1,3-diamide derivative to the hexahydropyrimidine (HHP) derivative is given. This work is thus instructive for understanding Fe(iii)-based tandem catalysis for the amidomethylative multiple-substitution reactions of alkenes. The Royal Society of Chemistry 2022-07-15 /pmc/articles/PMC9284522/ /pubmed/35919169 http://dx.doi.org/10.1039/d2ra02727e Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Cheng, Yaxuan Yang, Siwei Zhao, Chaoyu Liu, Huiling Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study |
title | Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study |
title_full | Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study |
title_fullStr | Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study |
title_full_unstemmed | Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study |
title_short | Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study |
title_sort | mechanism of the fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a dft study |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9284522/ https://www.ncbi.nlm.nih.gov/pubmed/35919169 http://dx.doi.org/10.1039/d2ra02727e |
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