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Syntheses of Tetrapyrroles

  • Kevin M. Smith
Protocol
  • 4.8k Downloads
Part of the Springer Protocols Handbooks book series (SPH)

Abstract

This chapter addresses basic methodology that can be used to obtain tetrapyrrole macrocycles in the porphyrin and chlorin series from natural materials and some simple methods for the total chemical synthesis of typical pyrroles and porphyrins. The aim is to provide investigators with enough information to decide whether to take on the task of preparing samples of useful porphyrin and chlorophyll derivatives or whether to simply purchase them or collaborate with other individuals more expert in the established synthetic procedures. The procedures reported herein are usually those which are easiest for the nonexpert to perform, while at the same time being sufficient to provide pure samples of the required product.

Keywords

Dimethyl Ester Lithium Aluminum Hydride Chlorophyll Derivative Sodium Amalgam Trimethyl Ester 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

References

  1. 1.
    Adler, A.D., F.R. Longo, J.D. Finarelli, J. Goldmacher, J. Assour, and L. Korsakoff. 1967. A simplified synthesis for meso-tetraphenylporphyrin. J. Org. Chem. 32:476.CrossRefGoogle Scholar
  2. 2.
    Aoyagi, K., T. Haga, H. Toi, Y. Aoyama, T. Mizutani, and H. Ogoshi. 1997. Electron deficient porphyrins. III. Facile syntheses of perfluoroalkylporphyrins including water soluble porphyrin. Bull. Chem. Soc. Jpn. 70:937–943.CrossRefGoogle Scholar
  3. 3.
    Arsenault, G.P., E. Bullock, and S.F. MacDonald. 1960. Pyrromethanes and porphyrins therefrom. J. Am. Chem. Soc. 82:4384–4389.CrossRefGoogle Scholar
  4. 4.
    Badger, G.M., R.A. Jones, and R.L. Laslett. 1964. Porphyrins. VII. The synthesis of porphyrins by the Rothemund reaction. Aust. J. Chem. 17:1028–1035.CrossRefGoogle Scholar
  5. 5.
    Baltazzi, E. and L.I. Krimen. 1963. Recent advances in the chemistry of pyrrole. Chem. Rev. 63:511.CrossRefGoogle Scholar
  6. 6.
    Barnett, G.H., M.F. Hudson, and K.M. Smith. 1975. Concerning meso-tetraphenylporphyrin purification. J. Chem. Soc. [Perkin 1] 1401–1403.Google Scholar
  7. 7.
    Barrett, J. 1959. Detection of hydroxyl groups in porphyrins and chlorins. Nature 183:1185–1186.PubMedCrossRefGoogle Scholar
  8. 8.
    Barton, D.H.R., J. Kervagoret, and S.Z. Zard. 1990. A useful synthesis of pyrroles from nitroolefins. Tetrahedron 46:7587–7598.CrossRefGoogle Scholar
  9. 9.
    Battersby, A.R. and E. McDonald. 1975. Biosynthesis of porphyrins, chlorins, and corrins. In K.M. Smith (Ed.), Porphyrins and Metalloporphyrins. Elsevier, Amsterdam.Google Scholar
  10. 10.
    Bonnett, R., I.H. Campion-Smith, and A.J. Page. 1977. Protiodevinylation: the Schumm reaction of vinylporphyrins. J. Chem. Soc. [Perkin 1]:68–71.Google Scholar
  11. 11.
    Bullock, E., A.W. Johnson, E. Markham, and K.B. Shaw. 1958. A synthesis of coproporphyrin III. J. Chem. Soc. 1430–1440.Google Scholar
  12. 12.
    Burbidge, P.A., G.L. Collier, A.H. Jackson, and G.W. Kenner. 1967. Syntheses and spectra of some meso-methylated porphyrins. J. Chem. Soc. B 930–937.Google Scholar
  13. 13.
    Cavaleiro, J.A.S., A.M.d’A.R. Gonsalves, G.W. Kenner, and K.M. Smith. 1973. Synthesis of pyrromethanes and a tripyrrane. J. Chem. Soc. [Perkin 1] 2471–2478.Google Scholar
  14. 14.
    Cavaleiro, J.A.S., A.M.d’A.R. Gonsalves, G.W. Kenner, and K.M. Smith. 1974. Total synthesis of deuteriated derivatives of protoporphyrin-IX for NMR studies of haemoproteins. J. Chem. Soc. [Perkin 1] 1771–1781.Google Scholar
  15. 15.
    Cavaleiro, J.A.S., G.W. Kenner, and K.M. Smith. 1974. Biosynthesis of protoporphyrin-IX from copro-porphyrinogen-III. J. Chem. Soc. [Perkin 1] 1188–1194.Google Scholar
  16. 16.
    Chu, T.C. and E.J.-H. Chu. 1955. Paper chromatography of iron complexes of porphyrins. J. Biol. Chem. 212:1–7.PubMedGoogle Scholar
  17. 17.
    DiNello, R.K. and D.H. Dolphin. 1981. Evidence for a fast (major) and slow (minor) pathway in the Schumm devinylation reaction of vinylporphyrins. J. Org. Chem. 46:3498–3502.CrossRefGoogle Scholar
  18. 18.
    cf. Eisner, U., A. Lichtarowicz, and R.P. Linstead. 1957. Chlorophylls and related compounds. Part VI. The synthesis of octaethylchlorin. J. Chem. Soc. 733–739.Google Scholar
  19. 19.
    Fischer, H. 1955. Preparation of hemin. Org. Synth. 3:442.Google Scholar
  20. 20.
    Fischer, H. and H. Orth. 1934. Die Chemie des Pyrrols. Vol. 1. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  21. 21.
    Fischer, H. and H. Orth. 1934. Die Chemie des Pyrrols. Vol. 1, p. 333. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  22. 22.
    Fischer, H. and H. Orth. 1937. Die Chemie des Pyrrols. Vol. 2, part 1. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  23. 23.
    Fischer, H. and H. Orth. 1937. Die Chemie des Pyrrols. Vol. 2, part 1, p 358. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  24. 24.
    Fischer, H. and A. Stern. 1940. Die Chemie des Pyrrols. Vol. 2, part 2. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  25. 25.
    Fischer, H. and A. Stern. 1940. Die Chemie des Pyrrols. Vol. 2, part 2, p. 48. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  26. 26.
    Fischer, H. and A. Stern. 1940. Die Chemie des Pyrrols. Vol. 2, part 2, p. 52. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  27. 27.
    Fischer, H. and A. Stern. 1940. Die Chemie des Pyrrols. Vol. 2, part 2, p. 73. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  28. 28.
    Fischer, H. and A. Stern. 1940. Die Chemie des Pyrrols. Vol. 2, part 2, p. 108. Akademische Verlagsgesellschaft, Leipzig.Google Scholar
  29. 29.
    Fischer, H. and K. Zeile. 1929. Synthese des haematoporphyrins, protoporphyrins und haemins. Liebigs Ann. Chem. 468:98–116.CrossRefGoogle Scholar
  30. 30.
    Freeman, B.A. and K.M. Smith. 1995. Novel uses of a naturally occurring heterogeneous catalyst to improve organic syntheses. Proc. NOBCChE 22:227–242.Google Scholar
  31. 31.
    Gerlach, B., S.E. Brantley, and K.M. Smith. 1998. Novel synthetic routes to 8-vinyl chlorophyll derivatives. J. Org. Chem. 63:2314–2320.CrossRefGoogle Scholar
  32. 32.
    Gossauer, A. 1974. Die Chemie der Pyrrole. Springer, Berlin.Google Scholar
  33. 33.
    Grinstein, M. 1947. Studies of protoporphyrin. J. Biol. Chem. 167:515–519.PubMedGoogle Scholar
  34. 34.
    Iakovides, P. and K.M. Smith. 1996. Syntheses of oxygen analogues of sulfhemes-A and-C. Tetrahedron 52:1123–1148.CrossRefGoogle Scholar
  35. 35.
    Inhoffen, H.H., J.-H. Fuhrhop, H. Voigt, and H. Brockmann, Jr. 1966. Formylierung der meso-Kohlenstoffeatome von alkylsubstituierten porphyrinen. Liebigs Ann. Chem. 695:133.CrossRefGoogle Scholar
  36. 36.
    Jackson, A.H., R.K. Pandey, K.R.N. Rao, and E. Roberts. 1985. Reactions on solid supports, part II: a convenient method for synthesis of pyrromethanes using a Montmorillonite clay as catalyst. Tetrahedron Lett. 26:793–796.CrossRefGoogle Scholar
  37. 37.
    Jackson, A.H. and K.M. Smith. 1973. In J.W. ApSimon (Ed.), Total Synthesis of Natural Products, Vol. 1, p. 143–278. John Wiley & Sons, New York.Google Scholar
  38. 38.
    Jackson, A.H. and K.M. Smith. 1984. In J.W. ApSimon (Ed.) Total Synthesis of Natural Products Vol. 6, p. 237–280. John Wiley & Sons, New York.Google Scholar
  39. 39.
    Kadish, K., K.M. Smith, and R. Guilard. (Eds.). 1999. The Porphyrin Handbook. Academic Press, Boston.Google Scholar
  40. 40.
    Kenner, G.W., S.W. McCombie, and K.M. Smith. 1973. Protection of porphyrin vinyl groups. A synthesis of coproporphyrin-III from protoporphyrin-IX. Liebigs Ann. Chem. 1329–1338.Google Scholar
  41. 41.
    Kenner, G.W., S.W. McCombie, and K.M. Smith. 1973. Separation and oxidative degradation of chlorophyll derivatives. J. Chem. Soc. [Perkin 1]. 2517–2523.Google Scholar
  42. 42.
    Kenner, G.W., J.M.E. Quirke, and K.M. Smith. 1976. Transformations of protoporphyrin-K into harderoprophyrin, pemptoporphyrin, chlorocruoroporphyrin and their isomers. Tetrahedron 32:2753–2756.CrossRefGoogle Scholar
  43. 43.
    Kleinspehn, G.G. 1955. Pyrrole series XXVII. Novel route to certain 2-pyrrolecarboxylic esters and nitriles. J. Am. Chem. Soc. 77:1546–1548.CrossRefGoogle Scholar
  44. 44.
    Labbe, R.F. and G. Nishida. 1957. A new method of hemin isolation. Biochim. Biophys. Acta 26:437.PubMedCrossRefGoogle Scholar
  45. 45.
    Lee, S.-J.H., N. Jagerovic, and K.M. Smith. 1993. Use of the chlorophyll derivative, purpurin-18, for syntheses of sensitizers for photodynamic therapy. J. Chem. Soc. [Perkin 1] 2369–2377.Google Scholar
  46. 46.
    Lemberg, R., B. Bloomfield, R. Caiger, and W. Lock-wood. 1955. Porphyrins with formyl groups. V. Isolation of porphyrin a from heart muscle and determination of its heme a content. Aust. J. Exp. Biol. Med. Sci. 33:435–450.PubMedCrossRefGoogle Scholar
  47. 47.
    Lindsey, J.S. 1999. Synthesis of meso-substituted porphyrins. In K. Kadish, K.M. Smith, and R. Guilard (Eds.), The Porphyrin Handbook, Chapter 2. Academic Press, Boston.Google Scholar
  48. 48.
    Lindsey, J.S., I.C. Schreiman, H.C. Hsu, RC. Kearney, and A.M. Marguerettaz. 1987. Rothemund and Adler-Longo reactions revisited: synthesis of tetraphenyl-porphyrins under equilibrium conditions. J. Org. Chem. 82:827–836.CrossRefGoogle Scholar
  49. 49.
    Mauzerall, D. 1960. The thermodynamic stability of porphyrinogens. J. Am. Chem. Soc. 52:2601–2605.CrossRefGoogle Scholar
  50. 50.
    Mironov, A.F., T.R. Ovsepyan, R.P. Evstigneeva, and N.A. Preobrazenskii. 1965. Synthetic studies in the dipyrrylmethane series. Synthesis of 4,4′-dimethyl-3,3′-bis(β-carbomethoxyethyl)dipyrrylmethane. Zh. Obshch. Khim. 35:324–328.Google Scholar
  51. 51.
    Morell, D.B., J. Barrett, and P.S. Clezy. 1961. The prosthetic groups of cytochrome oxidase. 1. Purification as porphyrin a and conversion into haemin a. Biochem. J. 78:793–797.PubMedGoogle Scholar
  52. 52.
    Morell, D.B. and M. Stewart. 1956. Removal of iron from hemins. Aust. J. Exp. Biol. Med. Sci. 34:211–218.PubMedCrossRefGoogle Scholar
  53. 53.
    Nguyen, L.T., M.O. Senge, and K.M. Smith. 1996. Simple methodology for syntheses of porphyrins possessing multiple peripheral substituents with an element of symmetry. J. Org. Chem. 67:998–1003.CrossRefGoogle Scholar
  54. 54.
    Nguyen, L.T. and K.M. Smith. 1996. Syntheses of type-I porphyrins via monopyrrole tetramerization. Tetrahedron Lett. 37:7177–7180.CrossRefGoogle Scholar
  55. 55.
    Ono, N., H. Kawamura, M. Bougauchi, and K. Maruyama. 1990. Porphyrin synthesis from nitrocompounds. Tetrahedron 46:7483–7496.CrossRefGoogle Scholar
  56. 56.
    Ono, M., R. Lattmann, K. Imomota, C. Lehmann, T. Friih, and, A. Eschenmoser. 1985. Monopyrrole precursors for the synthesis of uroporphyrinogenoctani-trile. Croat. Chem. Acta 58:627.Google Scholar
  57. 57.
    Rothemund, P. 1935. Formation of porphyrins from pyrrole and aldehydes. J. Am. Chem. Soc. 57:2010–2011.CrossRefGoogle Scholar
  58. 58.
    Rothemund, P. and A.R. Menotti. 1941. Porphyrin studies. IV. The synthesis of α,β,ρ,δ-tetraphenylpor-phyrin. J. Am. Chem. Soc. 63:267–270.CrossRefGoogle Scholar
  59. 59.
    Schreiber, J., H. Maag, N. Hashimoto, and A. Eschenmoser. 1971. Dimethyl(methylene)ammonium iodide. Angew. Chem. Int. Ed. Engl. 10:330–331.CrossRefGoogle Scholar
  60. 60.
    Schumm, O.Z. 1928. Preparation of hemin derivatives by pyro reactions. Z. Physiol. Chem. 178:1–18.Google Scholar
  61. 61.
    Sessler, J.L., A. Mozaffari, and M.R. Johnson. 1991. 3,4-Diethylpyrrole and 2,3,7,8,12,13,17,18-octaethyl-porphyrin. Org. Synth. 70:68–78.Google Scholar
  62. 62.
    Shiau, F.-Y., R.K. Pandey, S. Ramaprasad, T.J. Dougherty, and K.M. Smith. 1990. The isomeric mono-acetyl-mono-(l-hydroxyethyl)-deuteroporphyrins: synthesis, characterization and use for syntheses of regioselectively methyl-and vinyl-deuterated hemins. J. Org. Chem. 55:2190–2195.CrossRefGoogle Scholar
  63. 63.
    cf. Siedel, W. and F. Winkler. 1943. Oxydation von pyrrolderivaten mit bleitetraacetat. Liebigs Ann. Chem. 554:162–201.CrossRefGoogle Scholar
  64. 64.
    Smith, K.M. (Ed.). 1975. Porphyrins and Metalloporphyrins. Elsevier, Amsterdam.Google Scholar
  65. 65.
    Smith, K.M., G.M.F. Bisset, and M.J. Bushell. 1980. Partial syntheses of optically pure methyl bacterio-pheophorbides c and d from methyl pheophorbide a. J. Org. Chem. 45:2218–2224.CrossRefGoogle Scholar
  66. 66.
    Smith, K.M., E.M. Fujinari, K.C. Langry, D.W. Parish, and H.D. Tabba. 1983. Manipulation of vinyl groups in protoporphyrin-IX: introduction of deuterium and carbon-13 labels for spectroscopic studies. J. Am. Chem. Soc. 105:6638–6646.CrossRefGoogle Scholar
  67. 67.
    Smith, K.M., D.A. Goff, and D.J. Simpson. 1985. Meso-substitution of chlorophyll derivatives: direct route for transformation of bacteriopheophorbides-d into bacteriopheophorbides-c. J. Am. Chem. Soc. 107:4946–4954.CrossRefGoogle Scholar
  68. 68.
    Strain, H.H. and W.A. Svec. 1966. In L.P. Vernon and G.R. Seely (Eds.), p. 21. The Chlorophylls, Academic Press, New York.Google Scholar
  69. 69.
    Thudichum, J.L.W. 1867. Rpt. Med. Off. Privy Council, App. 7. 10:152.Google Scholar
  70. 70.
    Whitlock, H.W. and R. Hanauer. 1968. Octaethylporphyrin. J. Org. Chem. 33:2169–2171.CrossRefGoogle Scholar

Copyright information

© Humana Press, Totowa, NJ 2002

Authors and Affiliations

  • Kevin M. Smith
    • 1
  1. 1.Department of ChemistryUniversity of California-DavisDavisUSA

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