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Volumn 50, Issue 52, 2011, Pages 12412-12472

Etiology of potentially primordial biomolecular structures: From vitamin B 12 to the nucleic acids and an inquiry into the chemistry of life's origin: A retrospective

Author keywords

biogenesis; etiology; natural products; nucleic acids; vitamin B 12

Indexed keywords

BIOGENESIS; BIOMOLECULAR STRUCTURES; ETIOLOGY; EXPERIMENTAL MODELING; NATURAL PRODUCTS; ORIGIN OF LIFE; SHORTEST PATH; VITAMIN B; VITAMIN B 12;

EID: 84255198819     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201103672     Document Type: Review
Times cited : (136)

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    • 2) from calcium carbide and molecular nitrogen at temperatures over 1000 °C, or the Lassaigne test that the older generation of chemists may still remember (fusion of organic material with metallic sodium, plunging everything into water, and then testing for cyanide). The question of whether the Earth's crust could have been a source of organics relevant to the origin of life is addressed to the earth sciences, and only secondarily to chemistry. If such a scenario could not be positively excluded, the question posed would be of considerable etiological interest. The nearest counterargument, namely that no geochemical traces of such "reservoirs of organic material" are found today, would certainly not-after billions of years of a "hydrolyzing" earth history-be a valid reason for negating the question. (for previous comments on this subject cf. Figure 36 in Origins Life Evol. Biosphere 2004, 34, 277; and ref. [252]).
    • (2004) Origins Life Evol. Biosphere , vol.34 , pp. 277
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    • The statement refers to the condensation of 6,7-dimethyl-8- D -ribityl-lumazine with itself to produce riboflavin with concomitant re-formation of one equivalent of 5-amino-6- D -ribitylaminouracil, the molecule that happens to be the precursor of that very lumazine. This uracil derivative produces the lumazine by condensation with either 2,3-dioxobutane or 3,4-dihydroxy-2-butanone-4-phosphate, or even ribulose-1,5-diphosphate. The uracil derivative, the lumazine derivative and the dihydroxy-2-butanone derivative are intermediates in the biosynthesis of riboflavin; the two overall reaction steps that connect them have been shown also to occur non-enzymatically, the riboflavin-producing step (simple heating of the lumazine derivative in aqueous solution) displaying marvelously complex chemistry [cf. the work of H. C. S. Wood
    • The statement refers to the condensation of 6,7-dimethyl-8- D -ribityl-lumazine with itself to produce riboflavin with concomitant re-formation of one equivalent of 5-amino-6- D -ribitylaminouracil, the molecule that happens to be the precursor of that very lumazine. This uracil derivative produces the lumazine by condensation with either 2,3-dioxobutane or 3,4-dihydroxy-2-butanone-4-phosphate, or even ribulose-1,5-diphosphate. The uracil derivative, the lumazine derivative and the dihydroxy-2-butanone derivative are intermediates in the biosynthesis of riboflavin; the two overall reaction steps that connect them have been shown also to occur non-enzymatically, the riboflavin-producing step (simple heating of the lumazine derivative in aqueous solution) displaying marvelously complex chemistry [cf. the work of H. C. S. Wood (, T. Patterson, H. C. S. Wood, J. Chem. Soc. Chem. Commun. 1969, 290
    • (1969) J. Chem. Soc. Chem. Commun. , pp. 290
    • Patterson, T.1    Wood, H.C.S.2
  • 490
    • 0035917362 scopus 로고    scopus 로고
    • and the dissertation of C. Strupp (thesis. ETH, Nr. 9832, 1992); for structural formulas see Figure 9 of ref. [126].
    • K. Kis, K. Kugelbrey, A. Bacher, J. Org. Chem. 2001, 66, 2555), and the dissertation of C. Strupp (thesis. ETH, Nr. 9832, 1992); for structural formulas see Figure 9 of ref. [126].
    • (2001) J. Org. Chem. , vol.66 , pp. 2555
    • Kis, K.1    Kugelbrey, K.2    Bacher, A.3
  • 491
    • 0040981266 scopus 로고    scopus 로고
    • Whereas the biosynthetic pathway to riboflavin is-while mechanistically complex-clearly "chemomimetic" and, therefore, ultimately "simple", the pathways leading to thiamin uncovered thus far (see, e.g.
    • Whereas the biosynthetic pathway to riboflavin is-while mechanistically complex-clearly "chemomimetic" and, therefore, ultimately "simple", the pathways leading to thiamin uncovered thus far (see, e.g., I. D. Spenser, R. L. White, Angew. Chem. 1997, 109, 1096
    • (1997) Angew. Chem. , vol.109 , pp. 1096
    • Spenser, I.D.1    White, R.L.2
  • 493
    • 33644989816 scopus 로고    scopus 로고
    • and to pyridoxal (see, e.g.
    • T. P. Begley, Nat. Prod. Rep. 2006, 23, 15) and to pyridoxal (see, e.g.
    • (2006) Nat. Prod. Rep. , vol.23 , pp. 15
    • Begley, T.P.1
  • 494
    • 77953381350 scopus 로고    scopus 로고
    • are-in part-of extraordinary chemical complexity. Such a degree of complexity in a biosynthetic pathway to a potentially primordial biomolecule may be a hint at a scenario in which the molecule (or one of its type) would have fulfilled a catalytic role before its biosynthesis became established, which (in the extreme case) means that it may have been formed pre-biotically. Extraordinary complexity of biosynthetic pathway might reflect extraordinary evolutionary pressure that acted upon the emergence of biosynthetic access to a primordially pre-existing molecule (or its structural type), the functional potential of which was essential to the system's evolution (cf. for example, ref. [17]). As regards the structural type and/or function of thiamine and pyridoxal, demonstrating the existence of potentially prebiotic pathways to these molecules remains an open challenge.
    • T. B. Fitzpatrick, C. Moccand, C. Roux, ChemBioChem 2010, 11, 1185) are-in part-of extraordinary chemical complexity. Such a degree of complexity in a biosynthetic pathway to a potentially primordial biomolecule may be a hint at a scenario in which the molecule (or one of its type) would have fulfilled a catalytic role before its biosynthesis became established, which (in the extreme case) means that it may have been formed pre-biotically. Extraordinary complexity of biosynthetic pathway might reflect extraordinary evolutionary pressure that acted upon the emergence of biosynthetic access to a primordially pre-existing molecule (or its structural type), the functional potential of which was essential to the system's evolution (cf. for example, ref. [17]). As regards the structural type and/or function of thiamine and pyridoxal, demonstrating the existence of potentially prebiotic pathways to these molecules remains an open challenge.
    • (2010) ChemBioChem , vol.11 , pp. 1185
    • Fitzpatrick, T.B.1    Moccand, C.2    Roux, C.3


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