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Synthesis of 5,15-diaryltetrabenzoporphyrins

Journal

JOURNAL OF ORGANIC CHEMISTRY
Volume 73, Issue 11, Pages 4175-4185

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jo800509k

Keywords

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Funding

  1. NHLBI NIH HHS [R01 HL081273-01A1, R01 HL081273, HL 081273, R01 HL081273-03, R01 HL081273-02] Funding Source: Medline
  2. NIBIB NIH HHS [R01 EB007279, EB 007279, R01 EB007279-02] Funding Source: Medline
  3. NINDS NIH HHS [R01 NS031465-14, R01 NS031465, R01 NS031465-15, R01 NS031465-13A2] Funding Source: Medline

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A general method of synthesis of 5,15-diaryltetrabenzoporphyrins (Ar(2)TBPs) has been developed, based on 2 + 2 condensation of dipyrromethanes followed by oxidative aromatization. Two pathways to Ar(2)TBPs were investigated: the tetrahydroisoindole pathway and the dihydroisoindole pathway. In the tetrahydroisoindole pathway, precursor 5,15-diaryltetracyclohexenoporphyrins (5,15-Ar(2)TCHPs) were assembled from cyclohexeno-fused meso-unsubstituted dipyrromethanes and aromatic aldehydes or, alternatively, by way of the classical MacDonald synthesis. In the first case, scrambling was observed. Aromatization by tetracyclone was more effective than aromatization by DDQ but failed in the cases of porphyrins with electron-withdrawing substituents in the meso-aryl rings. The dihydroisoindole pathway was found to be much superior to the tetrahydroisoindole pathway, and it was developed into a general preparative method, consisting of (1) the synthesis of 4,7-dihydroisoindole and its transformation into meso-unsubstituted dipyrromethanes, (2) the synthesis of 5,15-diaryloctahydrotetrabenzoporphyrins (5,15-Ar(2)OHTBPs), and (3) their subsequent aromatization by DDQ. Ar2TBP free bases exhibit optical absorption spectra similar to those of meso-unsubstituted tetrabenzoporphyrins and fluoresce with high quantum yields. Pd complex of Ph2TBP was found to be highly phosphorescent at room temperature.

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