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

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    41 Citations (Scopus)

    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.

    Original languageEnglish
    Pages (from-to)4037-4050
    Number of pages14
    JournalTetrahedron
    Volume64
    Issue number18
    DOIs
    Publication statusPublished - Apr 28 2008

    All Science Journal Classification (ASJC) codes

    • Biochemistry
    • Drug Discovery
    • Organic Chemistry

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