Summary
Uro'gen-III is a key intermediate on the biosynthetic pathways to the vitally important natural pigments haem, chlorophyll and the cytochromes. How the unexpected structure of uro'gen-III is synthesized by living things has long been a major puzzle. Studies based on13C-labelling are described which show a) that a single intramolecular rearrangement occurs and b) that this step occurs after the open-chain linear tetrapyrrole system has been built.
A second study involves stereospecific labelling with deuterium and tritium to elucidate the absolute stereochemistry of the enzymic reaction sequence which produces the vinyl groups of haem. The third and last section of the lecture is focussed on the biosynthetic intermediates lying between uro'gen-III and cobyrinic acid on the pathway to vitamin B12. An octacarboxylic isobacteriochlorin is isolated from a vitamin B12-producing organism and this is shown to be identical with sirohydrochlorin, previously obtained by Kamin and Siegel as the metal-free prosthetic group of certain sulphite-reducing bacteria. The structure and absolute stereochemistry of sirohydrochlorin are studied and comment is made on the evolutionary interest of these findings.
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References
Reviewed by A. R. Battersby and E. McDonald in: Porphyrins and Metalloporphyrins, 2nd ed., p. 61. Ed. K. M. Smith. Elsevier, Amsterdam, 1975.
A. R. Battersby, E. Hunt, E. McDonald and J. Moron, J. Chem. Soc. Perkin I1973, 2917.
A. R. Battersby, G. L. Hodgson, M. Ihara, E. McDonald and J. Saunders, J. Chem. Soc. Perkin I1973, 2923.
A. R. Battersby, J. Staunton, E. McDonald, J. R. Redfern and R. H. Wightman, J. chem. Soc. Perkin I1976, 266.
A. R. Battersby, G. L. Hodgson, E. Hunt, E. McDonald and J. Saunders, J. chem. Soc. Perkin I,1976, 273.
A. R. Battersby, M. Ihara, E. McDonald, J. Saunders and R. J. Wells, J. chem. Soc. Perkin I1976, 283.
A. R. Battersby, D. G. Buckley, G. L. Hodgson, R. E. Markwell and E. McDonald, in: High Pressure Liquid Chromatography in Clinical Chemistry. Academic Press, 1976.
A. H. Jackson, D. E. Games, P. Couch, J. R. Jackson, R. B. Belcher and S. G. Smith, Enzyme,17, 81 (1974); R. Poulson and W. J. Polglase, J. biol. Chem.250, 1269 (1975).
A. R. Battersby, E. McDonald, D. C. Williams and H. K. W. Wurziger, J. chem. Soc. chem. Commun.1977, 113.
H.-O. Dauner, G. Gunzer, I. Heger and G. Müller, Hoppe Seyler's Z. physiol. Chem.357, 147 (1976).
A. R. Battersby, C. J. R. Fookes and E. McDonald, unpublished work.
A. R. Battersby, E. McDonald and M. J. Meegan, unpublished work.
J. H. Mathewson and A. H. Corwin, J. Am. chem. Soc.83, 135 (1961).
A. R. Battersby, D. A. Evans, K. H. Gibson, E. McDonald and L. N. Nixon, J. chem. Soc. Perkin I1973, 1546.
A. R. Battersby, K. H. Gibson, E. McDonald, L. N. Mander, J. Moron and L. N. Nixon, J. chem. Soc. chem. Commun.1973, 768.
A. R. Battersby, J. F. Beck and E. McDonald, J. chem. Soc. Perkin I1974, 160.
A. R. Battersby, D. G. Buckley, E. McDonald and D. C. Williams, J. chem. soc. chem. Commun.1977, 115.
A. R. Battersby, D. W. Johnson, E. McDonald and D. C. Williams, J. chem. Soc. chem. Commun.1977, 117.
B. Frydman and R. B. Frydman, Accts chem. Res.8, 201 (1975).
A. I. Scott, K. S. Ho, M. Kajiwara and T. Takahashi, J. Am. chem. Soc.98, 1589 (1976).
A. R. Battersby, J. Baldas, J. Collins, D. H. Grayson, K. J. James and E. McDonald. J. C. S. chem. Commun.1972, 1265.
A. R. Battersby, 23rd Int. Congr Pure and Applied Chemistry, Special Lectures5, 1 (1971).
Z. Zaman, M. M. Abbound and M. Akhatar, J. chem. Soc. chem. Commun.1972, 1263.
W. S. Knowles, M. J. Sabacky, B. D. Vineyard and D. J. Weinkauff, J. Am. chem. Soc.97, 2567 (1975).
A. R. Battersby, R. H. Wightman, J. Staunton and K. R. Hanson, J. chem. Soc. Perkin I1972, 2355.
A. R. Battersby, J. B. Campbell and E. McDonald, unpublished work.
A. R. Battersby, E. McDonal, H. K. W. Wurziger, and (in part) K. J. James, J. chem. Soc. chem. Commun.1975, 493.
J. W. Cornforth, R. H. Cornforth, G. Popjak and L. Yengoyan, J. biol. Chem.241, 3970 (1966).
K. Bernhauer, F. Wagner, H. Michna P. Rapp and H. Vogelmann, Hoppe Seyler's Z. physiol. Chem.349, 1297 (1968).
C. E. Brown, D. Shemin and J. J. Katz, J. biol. chem.248, 8015 (1973) and references therein.
A. I. Scott, C. A. Townsend, K. Okada, M. Kajiwara, P. J. Whitman and R. J. Cushley, J. Am. chem. Soc.,94, 8267 (1972); and96, 8069 (1974); A. I. Scott, N. Georgopapadakou, K. S. Ho, S. Klioze, E. Lee, S. C. Lee, G. H. Temme III, C. A. Townsend and I. A. Armitage, J. Am. chem. Soc.97, 2548 (1975) and references therein.
M. Infield, C. A. Townsend and D. Arigoni, J. chem. Soc. chem. Commun.1976, 541.
H.-O. Dauner and G. Müller, Hoppe Seyler's Z. physiol. Chem.356, 1353 (1975).
A. R. Battersby, Masataka Ihara, E. McDonald and Janet R. Stephenson, J. chem. Soc. chem. Commun.1973, 404; A. R. Battersby, M. Ihara, E. McDonald and J. R. Stephenson, J. chem. Soc. chem. Commun.1974, 458; A. R. Battersby, M. Ihara, E. McDonald, F. Satoh, and D. C. Williams, J. chem. Soc. chem. Commun.1975, 436.
A. R. Battersby, M. Ihara, E. McDonald, J. R. Redfern-Stephenson and B. T. Golding, J. chem. Soc. Perkin I1977, 158;
A. R. Battersby, E. McDonald, Roger Hollenstein, M. Ihara, F. Satoh and D. C. Williams, J. chem. Soc. Perkin I1977, 166, and references therein.
V. Ya. Bykhovsky, N. I. Zaitseva and N. V. Bukin, Doklady Acad. Sci. USSR.,224, 1431 (1975); V. ya. Bykhovsky, N. I. Zaitseva, A. V. Umrikhina, and A. N. Yavorskaya, Priklad. Biokhim. Mikrobiol.12, 825 (1976); V. Ya. Bykhovsky, N. I. Zaitseva, Priklad. Biokhim. Microbiol.12, 365 (1976).
A. R. Battersby, E. McDonald, H. Morris, M. Thompson and D. C. Williams, V. Bykhovsky, Natalia Zaitseva and V. Bukin, Tetrahedron Lett,1977, 2217.
U. Eisner, J. chem. Soc. 3461 (1957); R. Bonnett, I. A. D. Gale and G. F. Stephenson, J. chem. Soc.C, 1967, 1168; H. Whitlock, R. Hanauer, M. Y. Oester and B. K. Bower, J. Am. chem. Soc.91, 7485 (1969); H.-H. Inhoffen, J. W. Buchler and R. Thomas, Tetrahedron Lett.1969, 1141.
R. Bonnett, J. R. Cannon, V. M. Clark, A. W. Johnson, L. F. J. Parker, E. L. Smith and A. R. Todd, J. chem. Soc.1957, 1158.
L. M. Siegel, M. J. Murphy and H. Kamin, J. biol. Chem.248, 251 (1973); M. J. Murphy and L. M. Siegel, J. biol. Chem.248, 6911 (1973); M. J. Murphy, L. M. Siegel, H. Kamin and D. Rosenthal, J. biol. Chem.248, 2801 (1973).
A. R. Battersby, K. Jones, E. McDonald, J. Robinson and H. Morris, Tetrahedron Lett.1977, 2213.
A. R. Battersby, E. McDonald and M. Thompson, unpublished work.
R. Deeg, H.-P. Kriemler, K.-H. Bergmann and G. Müller, Hoppe Seyler's Z. physiol. Chem.358, 339 (1977).
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This account is a slightly extended version of the Paul Karrer Lecture given on July 5th, 1977 at the University of Zürich.
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Battersby, A.R. The discovery of nature's biosynthetic pathways. Experientia 34, 1–13 (1978). https://doi.org/10.1007/BF01921870
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DOI: https://doi.org/10.1007/BF01921870