Substitution, dimerization, metalation, and ring-opening reactions of N-fused porphyrins

Tomoya Ishizuka, Shinya Ikeda, Motoki Toganoh, Ichiro Yoshida, Yuichi Ishikawa, Atsuhiro Osuka, Hiroyuki Furuta

研究成果: ジャーナルへの寄稿記事

36 引用 (Scopus)

抄録

A variety of reactions such as substitution, dimerization, rhenium(I) metalation, and ring-opening reactions of N-fused porphyrin (NFP) and optical properties of the products are presented. Palladium-catalyzed cross-coupling reactions under Suzuki or Stille conditions afford aryl and arylethynyl-substituted NFPs (12, 14) and an ethynyl-bridged dimer (15) from 3-bromo-substituted NFP (3b) in 40-98% yields. Treatment of NFP with silver(I) trifluoroacetate in CHCl3 affords a dimer (22) linked at both C21-positions of the fused rings and its bis-Re(I) metal complex (24) is synthesized. X-ray structures of the 3-trifluoromethyl and 3-phenyl NFP derivatives (9e and 12a) reveal the three-center hydrogen bondings in the core. All the new NFP derivatives display unique absorption spectra, and particularly, ethyne-bridged NFP-dimer (15) shows a remarkable bathochromic shift into a near-infrared region showing an absorption band at 1020 nm with tailing up to 1100 nm. Moreover, alkoxide nucleophiles convert NFP into NCP derivatives by the cleavage of C-N bond in the fused ring, which is useful for the preparation of various C3-substituted NCPs and C21,C21′-linked NCP dimers from NFPs.

元の言語英語
ページ(範囲)4037-4050
ページ数14
ジャーナルTetrahedron
64
発行部数18
DOI
出版物ステータス出版済み - 4 28 2008

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Dimerization
Porphyrins
Substitution reactions
Dimers
Derivatives
Absorption spectra
Rhenium
Trifluoroacetic Acid
Acetylene
Nucleophiles
Coordination Complexes
Cross Reactions
Tailings
Palladium
Hydrogen Bonding
Silver
Hydrogen bonds
Optical properties
X-Rays
Infrared radiation

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

これを引用

Substitution, dimerization, metalation, and ring-opening reactions of N-fused porphyrins. / Ishizuka, Tomoya; Ikeda, Shinya; Toganoh, Motoki; Yoshida, Ichiro; Ishikawa, Yuichi; Osuka, Atsuhiro; Furuta, Hiroyuki.

:: Tetrahedron, 巻 64, 番号 18, 28.04.2008, p. 4037-4050.

研究成果: ジャーナルへの寄稿記事

Ishizuka, Tomoya ; Ikeda, Shinya ; Toganoh, Motoki ; Yoshida, Ichiro ; Ishikawa, Yuichi ; Osuka, Atsuhiro ; Furuta, Hiroyuki. / Substitution, dimerization, metalation, and ring-opening reactions of N-fused porphyrins. :: Tetrahedron. 2008 ; 巻 64, 番号 18. pp. 4037-4050.
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abstract = "A variety of reactions such as substitution, dimerization, rhenium(I) metalation, and ring-opening reactions of N-fused porphyrin (NFP) and optical properties of the products are presented. Palladium-catalyzed cross-coupling reactions under Suzuki or Stille conditions afford aryl and arylethynyl-substituted NFPs (12, 14) and an ethynyl-bridged dimer (15) from 3-bromo-substituted NFP (3b) in 40-98{\%} yields. Treatment of NFP with silver(I) trifluoroacetate in CHCl3 affords a dimer (22) linked at both C21-positions of the fused rings and its bis-Re(I) metal complex (24) is synthesized. X-ray structures of the 3-trifluoromethyl and 3-phenyl NFP derivatives (9e and 12a) reveal the three-center hydrogen bondings in the core. All the new NFP derivatives display unique absorption spectra, and particularly, ethyne-bridged NFP-dimer (15) shows a remarkable bathochromic shift into a near-infrared region showing an absorption band at 1020 nm with tailing up to 1100 nm. Moreover, alkoxide nucleophiles convert NFP into NCP derivatives by the cleavage of C-N bond in the fused ring, which is useful for the preparation of various C3-substituted NCPs and C21,C21′-linked NCP dimers from NFPs.",
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