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

Masataka Nakahara; Kengo Hanaya; Takeshi Sugai; Shuhei Higashibayashi

doi:10.1002/open.202000310

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

Masataka Nakahara, Kengo Hanaya, Takeshi Sugai, Shuhei Higashibayashi

School of Pharmaceutical Sciences

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	627-629
Number of pages	3
Journal	ChemistryOpen
Volume	10
Issue number	6
DOIs	https://doi.org/10.1002/open.202000310
Publication status	Published - 2021 Jun

Keywords

[4+2] cycloaddition
density functional theory
pyridinium
reaction mechanism
stepwise

ASJC Scopus subject areas

Chemistry(all)

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10.1002/open.202000310

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title = "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 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.",

keywords = "[4+2] cycloaddition, density functional theory, pyridinium, reaction mechanism, stepwise",

author = "Masataka Nakahara and Kengo Hanaya and Takeshi Sugai and Shuhei Higashibayashi",

note = "Funding Information: This work was supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI Grant No. 20K05499 (S.H.). Part of the calculations was performed using Research Center for Computational Science, Okazaki, Japan. Publisher Copyright: {\textcopyright} 2021 The Authors. Published by Wiley-VCH GmbH",

year = "2021",

month = jun,

doi = "10.1002/open.202000310",

language = "English",

volume = "10",

pages = "627--629",

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AU - Nakahara, Masataka

AU - Hanaya, Kengo

AU - Sugai, Takeshi

AU - Higashibayashi, Shuhei

N1 - Funding Information: This work was supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI Grant No. 20K05499 (S.H.). Part of the calculations was performed using Research Center for Computational Science, Okazaki, Japan. Publisher Copyright: © 2021 The Authors. Published by Wiley-VCH GmbH

PY - 2021/6

Y1 - 2021/6

N2 - 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.

AB - 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.

KW - [4+2] cycloaddition

KW - density functional theory

KW - pyridinium

KW - reaction mechanism

KW - stepwise

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

Abstract

Keywords

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