The stepwise syntheses and characterization of a series of symmetrical and unsymmetrical bisporphyrins, bischlorins, and biscorroles, and of porphyrin-chlorin and porphyrin-corrole dyads possessing ethylene, phenyl, and stilbene linking units are described. The methodology for synthesis of 10-substituted corroles 2 and their cobalt complexes 9 via a,c-biladiene salts 1 was first developed, and then extended to provide biscorroles (e.g., 4 and 5) linked through the 10-positions with phenyl linker units. Using a similar methodology, phenyl-linked corrole-porphyrin dyads 28 and 30 were also prepared. By way of intermediate phenyl-linked unsymmetrical bisdipyrromethanes, a completely unsymmetrical heterobimetallic bisporphyrin system, 45, was synthesized. Low-valent titanium coupling (McMurry) reactions were used to prepared stilbene-linked bisdipyrromethanes (e.g., 46) which were subsequently transformed into stilbene-linked bisporphyrins (e.g., 48). McMurry cross-coupling reactions of porphyrins bearing p-formylphenyl substituents also afforded an unsymmetrically substituted bisporphyrinylstilbene, 60, as well as the corresponding homodimers 56 and 59. Likewise, McMurry cross-coupling of a p-formylphenyl-substituted porphyrin, 62, with a formylchlorin, 63, afforded a stilbene-linked bisporphyrin, 64, a bischlorin, 66, and a novel porphyrin-chlorin heterodimer, 65. All novel products were characterized by H-1 NMR, IV-vis, and mass spectroscopy and elemental analysis. X-ray structural information was also obtained for the zinc/nickel bisporphyrin 45 and for the bis-nickel porphyrin-chlorin 65.

Paolesse, R., Pandey, R.k., Forsyth, T.p., Jaquinod, L., Gerzevske, K.r., Nurco, D.j., et al. (1996). Stepwise syntheses of bisporphyrins, bischlorins, and biscorroles, and of porphyrin-chlorin and porphyrin-corrole heterodimers. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 118(16), 3869-3882 [10.1021/ja9541138].

Stepwise syntheses of bisporphyrins, bischlorins, and biscorroles, and of porphyrin-chlorin and porphyrin-corrole heterodimers

PAOLESSE, ROBERTO;LICOCCIA, SILVIA;
1996-01-01

Abstract

The stepwise syntheses and characterization of a series of symmetrical and unsymmetrical bisporphyrins, bischlorins, and biscorroles, and of porphyrin-chlorin and porphyrin-corrole dyads possessing ethylene, phenyl, and stilbene linking units are described. The methodology for synthesis of 10-substituted corroles 2 and their cobalt complexes 9 via a,c-biladiene salts 1 was first developed, and then extended to provide biscorroles (e.g., 4 and 5) linked through the 10-positions with phenyl linker units. Using a similar methodology, phenyl-linked corrole-porphyrin dyads 28 and 30 were also prepared. By way of intermediate phenyl-linked unsymmetrical bisdipyrromethanes, a completely unsymmetrical heterobimetallic bisporphyrin system, 45, was synthesized. Low-valent titanium coupling (McMurry) reactions were used to prepared stilbene-linked bisdipyrromethanes (e.g., 46) which were subsequently transformed into stilbene-linked bisporphyrins (e.g., 48). McMurry cross-coupling reactions of porphyrins bearing p-formylphenyl substituents also afforded an unsymmetrically substituted bisporphyrinylstilbene, 60, as well as the corresponding homodimers 56 and 59. Likewise, McMurry cross-coupling of a p-formylphenyl-substituted porphyrin, 62, with a formylchlorin, 63, afforded a stilbene-linked bisporphyrin, 64, a bischlorin, 66, and a novel porphyrin-chlorin heterodimer, 65. All novel products were characterized by H-1 NMR, IV-vis, and mass spectroscopy and elemental analysis. X-ray structural information was also obtained for the zinc/nickel bisporphyrin 45 and for the bis-nickel porphyrin-chlorin 65.
1996
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/07 - FONDAMENTI CHIMICI DELLE TECNOLOGIE
English
Con Impact Factor ISI
macrocyclic compound; porphyrin derivative; article; drug structure; drug synthesis; nuclear magnetic resonance; reaction analysis; spectrophotometry
Paolesse, R., Pandey, R.k., Forsyth, T.p., Jaquinod, L., Gerzevske, K.r., Nurco, D.j., et al. (1996). Stepwise syntheses of bisporphyrins, bischlorins, and biscorroles, and of porphyrin-chlorin and porphyrin-corrole heterodimers. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 118(16), 3869-3882 [10.1021/ja9541138].
Paolesse, R; Pandey, Rk; Forsyth, Tp; Jaquinod, L; Gerzevske, Kr; Nurco, Dj; Senge, Mo; Licoccia, S; Boschi, T; Smith, Km
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/53574
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