Facile Elaboration of Porphyrins via Metal-Mediated Cross-Coupling

Stephen G. DiMagno, Victor S.Y. Lin, Michael J. Therien

Research output: Contribution to journalArticle

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Abstract

Metal-mediated cross-coupling methodologies have been successfully employed to porphyrinic systems, providing a powerful, versatile, and general synthetic approach for the fabrication of elaborated porphyrin structures. A large number of coupling reactions have been carried out at two halogenated porphyrin templates, [2-bromo-5,10,15,20-tetraphenylporphinato]zinc and [5,15-dibromo-10,20-diphenylporphinato]zinc, generating a variety of porphyrins, 10 of which are novel: [2-n-butyl-5,-10,15,20-tetraphenylporphinato]zinc(II), [2-(2,5-dimethoxyphenyl)-5,10,15,20-tetraphenylporphinato]-zmc(II),[2-(9-anthracenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [2-vinyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2,5,10,15,20-pentaphenylporphinato]zinc(II), [2-isobutyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2-(pentafluorophenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [5,15-bis-[[2-(4′-methyl-2′-pyridyl)-4-pyridyl]methyl]-10,20-diphenylporphinato]zinc(II), [5,15-divmyl-10,20-diphenylporphinato]zinc(II), [5,15-bis(2,5-dimethoxyphenyl)-10,20-diphenylporphinato]zinc(II), and [5,15-bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II). The structures of [2,5,10,15,20-pentaphenylporphinato]zinc(II) and 5,15-bis-(pentafluorophenyl)-10,20-diphenylporphyrin have been determined; X-ray data are as follows: P21/n with a = 21.425(4) Å, b = 9.718(1) Å, c = 24.905(2) Å, β = 110.83(1)°, V = 4846(3) Å3, dcalc = 1.260 g cm−3, and Z = 4 for the former; and P21/c with a = 15.223(2) Å, b = 10.162(1) Å, c = 12.375(2) Å, β = 112.75(2)°, V= 1765.6(9) Å3, dcalc = 1.495 g cm−3, and Z = 2 for thelatter. This study demonstrates that cross-coupling reactions at the porphyrin periphery are seemingly not subject to the steric or electronic constraints that often limit the scope of these reactions in simple aryl and vinyl systems.

Original languageEnglish (US)
Pages (from-to)5983-5993
Number of pages11
JournalJournal of Organic Chemistry
Volume58
Issue number22
DOIs
StatePublished - Jan 1 1993

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Porphyrins
Zinc
Metals

ASJC Scopus subject areas

  • Organic Chemistry

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Facile Elaboration of Porphyrins via Metal-Mediated Cross-Coupling. / DiMagno, Stephen G.; Lin, Victor S.Y.; Therien, Michael J.

In: Journal of Organic Chemistry, Vol. 58, No. 22, 01.01.1993, p. 5983-5993.

Research output: Contribution to journalArticle

DiMagno, Stephen G. ; Lin, Victor S.Y. ; Therien, Michael J. / Facile Elaboration of Porphyrins via Metal-Mediated Cross-Coupling. In: Journal of Organic Chemistry. 1993 ; Vol. 58, No. 22. pp. 5983-5993.
@article{084e0f5b47c148928047f0a133d9f8da,
title = "Facile Elaboration of Porphyrins via Metal-Mediated Cross-Coupling",
abstract = "Metal-mediated cross-coupling methodologies have been successfully employed to porphyrinic systems, providing a powerful, versatile, and general synthetic approach for the fabrication of elaborated porphyrin structures. A large number of coupling reactions have been carried out at two halogenated porphyrin templates, [2-bromo-5,10,15,20-tetraphenylporphinato]zinc and [5,15-dibromo-10,20-diphenylporphinato]zinc, generating a variety of porphyrins, 10 of which are novel: [2-n-butyl-5,-10,15,20-tetraphenylporphinato]zinc(II), [2-(2,5-dimethoxyphenyl)-5,10,15,20-tetraphenylporphinato]-zmc(II),[2-(9-anthracenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [2-vinyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2,5,10,15,20-pentaphenylporphinato]zinc(II), [2-isobutyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2-(pentafluorophenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [5,15-bis-[[2-(4′-methyl-2′-pyridyl)-4-pyridyl]methyl]-10,20-diphenylporphinato]zinc(II), [5,15-divmyl-10,20-diphenylporphinato]zinc(II), [5,15-bis(2,5-dimethoxyphenyl)-10,20-diphenylporphinato]zinc(II), and [5,15-bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II). The structures of [2,5,10,15,20-pentaphenylporphinato]zinc(II) and 5,15-bis-(pentafluorophenyl)-10,20-diphenylporphyrin have been determined; X-ray data are as follows: P21/n with a = 21.425(4) {\AA}, b = 9.718(1) {\AA}, c = 24.905(2) {\AA}, β = 110.83(1)°, V = 4846(3) {\AA}3, dcalc = 1.260 g cm−3, and Z = 4 for the former; and P21/c with a = 15.223(2) {\AA}, b = 10.162(1) {\AA}, c = 12.375(2) {\AA}, β = 112.75(2)°, V= 1765.6(9) {\AA}3, dcalc = 1.495 g cm−3, and Z = 2 for thelatter. This study demonstrates that cross-coupling reactions at the porphyrin periphery are seemingly not subject to the steric or electronic constraints that often limit the scope of these reactions in simple aryl and vinyl systems.",
author = "DiMagno, {Stephen G.} and Lin, {Victor S.Y.} and Therien, {Michael J.}",
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language = "English (US)",
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TY - JOUR

T1 - Facile Elaboration of Porphyrins via Metal-Mediated Cross-Coupling

AU - DiMagno, Stephen G.

AU - Lin, Victor S.Y.

AU - Therien, Michael J.

PY - 1993/1/1

Y1 - 1993/1/1

N2 - Metal-mediated cross-coupling methodologies have been successfully employed to porphyrinic systems, providing a powerful, versatile, and general synthetic approach for the fabrication of elaborated porphyrin structures. A large number of coupling reactions have been carried out at two halogenated porphyrin templates, [2-bromo-5,10,15,20-tetraphenylporphinato]zinc and [5,15-dibromo-10,20-diphenylporphinato]zinc, generating a variety of porphyrins, 10 of which are novel: [2-n-butyl-5,-10,15,20-tetraphenylporphinato]zinc(II), [2-(2,5-dimethoxyphenyl)-5,10,15,20-tetraphenylporphinato]-zmc(II),[2-(9-anthracenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [2-vinyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2,5,10,15,20-pentaphenylporphinato]zinc(II), [2-isobutyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2-(pentafluorophenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [5,15-bis-[[2-(4′-methyl-2′-pyridyl)-4-pyridyl]methyl]-10,20-diphenylporphinato]zinc(II), [5,15-divmyl-10,20-diphenylporphinato]zinc(II), [5,15-bis(2,5-dimethoxyphenyl)-10,20-diphenylporphinato]zinc(II), and [5,15-bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II). The structures of [2,5,10,15,20-pentaphenylporphinato]zinc(II) and 5,15-bis-(pentafluorophenyl)-10,20-diphenylporphyrin have been determined; X-ray data are as follows: P21/n with a = 21.425(4) Å, b = 9.718(1) Å, c = 24.905(2) Å, β = 110.83(1)°, V = 4846(3) Å3, dcalc = 1.260 g cm−3, and Z = 4 for the former; and P21/c with a = 15.223(2) Å, b = 10.162(1) Å, c = 12.375(2) Å, β = 112.75(2)°, V= 1765.6(9) Å3, dcalc = 1.495 g cm−3, and Z = 2 for thelatter. This study demonstrates that cross-coupling reactions at the porphyrin periphery are seemingly not subject to the steric or electronic constraints that often limit the scope of these reactions in simple aryl and vinyl systems.

AB - Metal-mediated cross-coupling methodologies have been successfully employed to porphyrinic systems, providing a powerful, versatile, and general synthetic approach for the fabrication of elaborated porphyrin structures. A large number of coupling reactions have been carried out at two halogenated porphyrin templates, [2-bromo-5,10,15,20-tetraphenylporphinato]zinc and [5,15-dibromo-10,20-diphenylporphinato]zinc, generating a variety of porphyrins, 10 of which are novel: [2-n-butyl-5,-10,15,20-tetraphenylporphinato]zinc(II), [2-(2,5-dimethoxyphenyl)-5,10,15,20-tetraphenylporphinato]-zmc(II),[2-(9-anthracenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [2-vinyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2,5,10,15,20-pentaphenylporphinato]zinc(II), [2-isobutyl-5,10,15,20-tetraphenylporphinato]zinc(II), [2-(pentafluorophenyl)-5,10,15,20-tetraphenylporphinato]zinc(II), [5,15-bis-[[2-(4′-methyl-2′-pyridyl)-4-pyridyl]methyl]-10,20-diphenylporphinato]zinc(II), [5,15-divmyl-10,20-diphenylporphinato]zinc(II), [5,15-bis(2,5-dimethoxyphenyl)-10,20-diphenylporphinato]zinc(II), and [5,15-bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II). The structures of [2,5,10,15,20-pentaphenylporphinato]zinc(II) and 5,15-bis-(pentafluorophenyl)-10,20-diphenylporphyrin have been determined; X-ray data are as follows: P21/n with a = 21.425(4) Å, b = 9.718(1) Å, c = 24.905(2) Å, β = 110.83(1)°, V = 4846(3) Å3, dcalc = 1.260 g cm−3, and Z = 4 for the former; and P21/c with a = 15.223(2) Å, b = 10.162(1) Å, c = 12.375(2) Å, β = 112.75(2)°, V= 1765.6(9) Å3, dcalc = 1.495 g cm−3, and Z = 2 for thelatter. This study demonstrates that cross-coupling reactions at the porphyrin periphery are seemingly not subject to the steric or electronic constraints that often limit the scope of these reactions in simple aryl and vinyl systems.

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