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Flexible BODIPY Platform That Offers an Unexpected Regioselective Heterocyclization Reaction toward Preparation of 2-Pyridone[a]-Fused BODIPYs

Author:
Didukh, Natalia O., Yakubovskyi, Viktor P., Zatsikha, Yuriy V., Rohde, Gregory T., Nemykin, Victor N., Kovtun, Yuriy P.
Source:
Journal of organic chemistry 2019 v.84 no.4 pp. 2133-2147
ISSN:
1520-6904
Subject:
X-ray diffraction, chemical reactions, fluorescence emission spectroscopy, moieties, organic chemistry, organic compounds, regioselectivity, ultraviolet-visible spectroscopy
Abstract:
We have explored the synthetic routes for regioselective formation of 2-pyridone[a]- and 2-pyridone[b]-fused BODIPYs using 1,3,5,7-tetramethyl-2,6-dicarbethoxy-BODIPY as the universal starting platform. While heterocyclization of the 3-(dimethylaminovinyl)-BODIPY and 3,5-bis(dimethylaminovinyl)-BODIPY results in the formation of mono-2-pyridone- and bis-2-pyridone[b]-fused BODIPYs, respectively, similar heterocyclization of the 1,3-bis(dimethylaminovinyl)-BODIPY leads to the regioselective formation of the 2-pyridone[a]-fused BODIPY core, which is the first example of heterocycle[a]-fused BODIPYs. The regioselective formation of the 2-pyridone[a]-fused BODIPY was further confirmed by X-ray crystallography and explained on the basis of the DFT and TDDFT calculations that are suggestive of the energy-favorable out-of-plane rotation of the dimethylaminovinyl group located at first position, which accelerates the reaction with n-butylamine. Trends in the UV–vis and fluorescence spectra of the BODIPYs 1–17 were discussed on the basis of DFT and TDDFT calculations.
Agid:
6310436