Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether

Abstract Dearomative heterocyclic [4+2] cycloaddition between the N‐(2,4‐dinitrophenyl)pyridinium ion of nicotinamide and an enol ether was analyzed by Density Functional Theory (DFT) calculations. The calculation revealed that the reaction undergoes stepwise bond formation rather than occurring in...

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Main Authors:	Masataka Nakahara, Prof. Kengo Hanaya, Prof. Takeshi Sugai, Prof. Shuhei Higashibayashi
Format:	Article
Language:	English
Published:	Wiley-VCH 2021-06-01
Series:	ChemistryOpen
Subjects:	[4+2] cycloaddition density functional theory pyridinium reaction mechanism stepwise
Online Access:	https://doi.org/10.1002/open.202000310

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spelling	doaj-57b5521f2067419b834e8d55c2e767bf2021-07-19T06:33:04ZengWiley-VCHChemistryOpen2191-13632021-06-0110662762910.1002/open.202000310Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol EtherMasataka Nakahara0Prof. Kengo Hanaya1Prof. Takeshi Sugai2Prof. Shuhei Higashibayashi3Department of Pharmaceutical Sciences, Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku, Tokyo 105-8512 JapanDepartment of Pharmaceutical Sciences, Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku, Tokyo 105-8512 JapanDepartment of Pharmaceutical Sciences, Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku, Tokyo 105-8512 JapanDepartment of Pharmaceutical Sciences, Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku, Tokyo 105-8512 JapanAbstract Dearomative heterocyclic [4+2] cycloaddition between the N‐(2,4‐dinitrophenyl)pyridinium ion of nicotinamide and an enol ether was analyzed by Density Functional Theory (DFT) calculations. The calculation revealed that the reaction undergoes stepwise bond formation rather than occurring in a concerted manner. The experimental products were found to be both kinetically and thermodynamically favored. The calculated transition states and intermediate suggested that the high diastereoselectivity is derived from the electrostatic interaction between the 2‐nitro group of the pyridinium ion and the hydrogen of the enol ether.https://doi.org/10.1002/open.202000310[4+2] cycloadditiondensity functional theorypyridiniumreaction mechanismstepwise
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Masataka Nakahara Prof. Kengo Hanaya Prof. Takeshi Sugai Prof. Shuhei Higashibayashi
spellingShingle	Masataka Nakahara Prof. Kengo Hanaya Prof. Takeshi Sugai Prof. Shuhei Higashibayashi Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether ChemistryOpen [4+2] cycloaddition density functional theory pyridinium reaction mechanism stepwise
author_facet	Masataka Nakahara Prof. Kengo Hanaya Prof. Takeshi Sugai Prof. Shuhei Higashibayashi
author_sort	Masataka Nakahara
title	Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_short	Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_full	Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_fullStr	Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_full_unstemmed	Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_sort	theoretical analysis of the heterocyclic [4+2] cycloaddition between pyridinium ion and enol ether
publisher	Wiley-VCH
series	ChemistryOpen
issn	2191-1363
publishDate	2021-06-01
description	Abstract Dearomative heterocyclic [4+2] cycloaddition between the N‐(2,4‐dinitrophenyl)pyridinium ion of nicotinamide and an enol ether was analyzed by Density Functional Theory (DFT) calculations. The calculation revealed that the reaction undergoes stepwise bond formation rather than occurring in a concerted manner. The experimental products were found to be both kinetically and thermodynamically favored. The calculated transition states and intermediate suggested that the high diastereoselectivity is derived from the electrostatic interaction between the 2‐nitro group of the pyridinium ion and the hydrogen of the enol ether.
topic	[4+2] cycloaddition density functional theory pyridinium reaction mechanism stepwise
url	https://doi.org/10.1002/open.202000310
work_keys_str_mv	AT masatakanakahara theoreticalanalysisoftheheterocyclic42cycloadditionbetweenpyridiniumionandenolether AT profkengohanaya theoreticalanalysisoftheheterocyclic42cycloadditionbetweenpyridiniumionandenolether AT proftakeshisugai theoreticalanalysisoftheheterocyclic42cycloadditionbetweenpyridiniumionandenolether AT profshuheihigashibayashi theoreticalanalysisoftheheterocyclic42cycloadditionbetweenpyridiniumionandenolether
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Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether

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