AI Article Synopsis
- N-alkylation alters the electronic and optical traits as well as the reactivity of nitrogen-containing π-conjugated molecules like 5,15-diazaporphyrins.
- Treating these molecules with methyl triflate yields N-methyl-5,15-diazaporphyrinium cations, significantly improving their electron-accepting ability due to a lower LUMO level.
- This N-methylation not only boosts acidity of inner NH protons but also facilitates selective Diels-Alder reactions and helps create nitrogen-substituted isoporphyrin analogues with a single NH group.
Article Abstract
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.
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| http://dx.doi.org/10.1002/chem.201905402 | DOI Listing |
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