Supramolecular Regioselectivity of meso-Phenylporphyrin Sulfonation. Synthesis of 5,10,15-Tris(4’-sulfophenyl)porphine

Vladimir B. Sheinin,^a@ Dmitriy A. Ivanov,^a and Oscar I. Koifman^a,b

Dedicated to Academician Aslan Yusupovich Tsivadze on the occasion of his Birthday

^aG.A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 153045 Ivanovo, Russia

^bIvanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia

^@Corresponding author E-mail: vbs@isc-ras.ru

DOI: 10.6060/mhc170833s

Macroheterocycles 2017 10(4-5) 487-495

The results of the prognostic computer synthesis of meso-phenylporphyrins Н₂Р(Ph)_n sulfo derivatives, which demonstrate the supramolecular nature of the porphyrins sulfonation regioselectivity in concentrated sulfuric acid and oleum, are presented. By means of DFT calculation it has been shown that regioselectivityof meso-phenylporphyrins sulfonation is due to host-guest complex formation of the diprotonated porphyrin platform with two hydrosulfate anions, [H₄P²⁺(Ph)_n](HSO₄^-)₂. The guest anions control the reactivity of H₄P²⁺(Ph)_n. First, they activate H₄P²⁺(Ph)_n for electrophilic substitution by partial negative charge transfer to the diprotonated porphyrin. Second, the guest anions are the cause of a total charges redistribution on the carbon atoms of H₄P²⁺ and the phenyl rings, thereby providing the regioselectivity of H₄P²⁺(Ph)_n sulfonation. The data from prognostic stage calculations and method of organic synthesis were used to obtain the new 5,10,15-tris(4’-sulfophenyl)porphine. The obtained results are comprehensive and applicable to other S_EAr reactions of porphyrins.

References:

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Supramolecular Regioselectivity of meso-Phenylporphyrin Sulfonation. Synthesis of 5,10,15-Tris(4’-sulfophenyl)porphine

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