Synthesis of a Series of Mono-meso-arylmesoporphyrins III of Biological Interest and Their Biliverdin Derivatives

Abstract

Synthesis of a series of mono-meso-arylmesoporphyrins III using a MacDonald-type 2+2 condensation is described. In this method, the substituted 1,9-diformyldipyrromethane is treated with a dipyrromethane-1,9-dicarboxylic acid under acidic conditions. The 5-aryldipyrrolic unit was obtained by condensation of tert-butyl, ethyl, or benzyl 4-ethyl-3-methyl-1H-pyrrole-2-carboxylate with different aromatic aldehydes in the presence of 4-toluenesulfonic acid. In order to obtain the corresponding mesobiliverdins, chemical oxidation of each mesoporphyrin was carried out. Each meso-arylmesoporphyrin rendered two isomeric arylbiliverdins, as the porphyrin meso-aryl bridge is not cleaved.

Key words

porphyrin synthesis - mono-meso-arylporphyrin - chem­ical oxidation - biliverdin

References

• 1 Tenhunen R. Marver HS. Schmid R. J. Biol. Chem.  1969,  244:  6388 
• 2 Ortiz de Montellano PR. Curr. Opin. Chem. Biol.  2000,  4:  221 ; and references therein
• 3 Torpey J. Ortiz de Montellano PR. J. Biol. Chem.  1996,  271:  26067 
• 4 Wang J. Niemevz F. Lad L. Huang L. Alvarez DE. Buldain GY. Poulos TL. Ortiz de Montellano PR. J. Biol. Chem.  2004,  279:  42593 
• 5 Arsenault GP. Bullock E. MacDonald SF. J. Am. Chem. Soc.  1960,  82:  4384 
• 6 Valasinas AL. Frydman B. J. Org. Chem.  1976,  41:  2991 
• 7 Robinsohn AE. Buldain GY. J. Heterocycl. Chem.  1995,  32:  1567 
• 8 Robinsohn AE. Maier MS. Buldain GY. Heterocycles  2000,  53:  2127 
• 9 Niemevz F. Lázaro Martínez JM. Carballo R. Rezzano I. Buldain GY. Synthesis  2006,  870 
• 10 Chen Q. Huggins MT. Lightner DA. Norona W. McDonagh AF. J. Am. Chem. Soc.  1999,  121:  9253 
• 11 Awruch J. Frydman B. Tetrahedron  1986,  42:  4137 
• 12 Daignault RA. Eliel EL. Org. Synth. Coll. Vol. V   John Wiley & Sons; London: 1973.  p.303 
• 13 Li T.-S. Li S.-H. Li J.-T. Li H.-Z. J. Chem. Res., Synop.  1997,  26 
• 14 Kleinfelter DC. J. Org. Chem.  1967,  32:  840 
• 15 Dusza JP. Joseph JP. Bernstein S. J. Am. Chem. Soc.  1964,  86:  3908 
• 16 Mironov AF. Ovsepyan TR. Evstigneeva RP. Preobrazhenskii NA. Zh. Obshch. Khim.  1965,  35:  324 
• 17 Fuhrhop J.-H. Smith KM. In Laboratory Methods in Porphyrin and Metalloporphyrin Research   Elsevier; Amsterdam: 1975.  p.44 
• 18 Sklyar Yu E. Evstigneeva RP. Preobrazhenskii NA. Khim. Geterotsikl. Soedin.  1965,  4:  633 
• 19a Niemevz F. Alvarez DE. Buldain GY. Heterocycles  2002,  57:  697 
• 19b Niemevz F. Buldain GY. J. Porphyrins Phthalocyanines  2004,  8:  989 
• 20 Bonnett R. McDonagh AF. J. Chem. Soc., Perkin Trans. 1  1973,  881 
• 21 Abraham RJ. Jackson AH. Kenner GW. Warburton GJ. J. Chem. Soc.  1963,  863