2024-03-29T08:15:13Z
https://nagoya.repo.nii.ac.jp/oai
oai:nagoya.repo.nii.ac.jp:00030129
2023-01-16T04:23:19Z
320:321:322
Site‐Selective N‐Methylation of 5,15‐Diazaporphyrins: Reactive Cationic Porphyrinoids that Provide Isoporphyrin Analogues
Chia, Wen Xi
99456
Nishijo, Mayu
99457
Kang, Seongsoo
99458
Oh, Juwon
99459
Nishimura, Tsubasa
99460
Omori, Hiroto
99461
Longevial, Jean‐François
99462
Miyake, Yoshihiro
99463
Kim, Dongho
99464
Shinokubo, Hiroshi
99465
aromaticity
conjugation
cycloaddition
methylation
porphyrinoids
N‐Alkylation significantly changes the electronic and optical properties, as well as the reactivity of nitrogen‐containing π‐conjugated molecules. In this study, it is found that treating 5,15‐diazaporphyrins with methyl triflate selectively affords the corresponding N ‐methyl‐5,15‐diazaporphyrinium cations in good yield. N‐Methylation substantially alters the electronic properties and reactivity of diazaporphyrins. The electron‐accepting properties of the N ‐methyl‐5,15‐diazaporphyrinium cations are enhanced due to their lowered LUMO level. Stabilization of the LUMO energy enables regio‐ and stereoselective Diels–Alder reactions of the cationic diazaporphyrin with cyclopentadiene. N‐Methylation also enhances the acidity of the inner NH protons, and thus, allows facile deprotonation to provide nitrogen‐substituted isoporphyrin analogues with only one NH group in the central cavity.
ファイル公開:2021-02-26
journal article
Wiley
2020-02-26
application/pdf
Chemistry–A European Journal
12
26
2754
2760
0947-6539
https://nagoya.repo.nii.ac.jp/record/30129/files/manuscript.pdf
eng
https://doi.org/10.1002/chem.201905402
This is the peer reviewed version of the following article: [W. X. Chia, M. Nishijo, S. Kang, J. Oh, T. Nishimura, H. Omori, J.-F. Longevial, Y. Miyake, D. Kim, H. Shinokubo, Chem. Eur. J. 2020 , 26 , 2754.], which has been published in final form at [https://doi.org/10.1002/chem.201905402]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.