Site-Selective N-Methylation of 5,15-Diazaporphyrins: Reactive Cationic Porphyrinoids that Provide Isoporphyrin Analogues.
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.
['Chia|Wen Xi|WX|', 'Nishijo|Mayu|M|', 'Kang|Seongsoo|S|', 'Oh|Juwon|J|', 'Nishimura|Tsubasa|T|', 'Omori|Hiroto|H|', 'Longevial|Jean-François|JF|', 'Miyake|Yoshihiro|Y|http://orcid.org/0000-0003-0247-531X', 'Kim|Dongho|D|http://orcid.org/0000-0001-8668-2644', 'Shinokubo|Hiroshi|H|http://orcid.org/0000-0002-5321-2205']
porphyrinoids methylation aromaticity conjugation cycloaddition