Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 14, Issue 1, Pages 204-211Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200701398
Keywords
cycloaddition; porphyrinoids; site-selectivity; X-ray diffraction
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A triply linked Zn-II diporphyrin underwent site-selective cyclo-addition reactions with thermally generated o-xylylene to provide a triply linked porphyrin-chlorin hybrid and a triply linked chlorin dimer in moderate yields. ne former product is a symmetry-allowed [4+2] cycloadduct, while the latter is a symmetry-forbidden [4+4] cycloadduct. Oxidation of the latter product with 2,3-dichloro-5,6-di-cyano-1,4-benzoquinone (DDQ) provided a triply linked diporphyrin fused with a benzocyclooctatriene segment. This oxidized product and above [4+2] cycloadduct were structurally characterized by single crystal X-ray diffraction analysis. The observed site-selectivity is considered to arise from the large MO coefficients at the bay-area in the LUMO of the triply linked diporphyrin. The anomalous thermal [4+4] cycloaddition may be ascribed to the highly conjugated and quite perturbed electronic properties of triply linked Zn-II diporphyrin.
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