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Total Synthesis, Structure, and Biological Activity of Adenosylrhodibalamin, the Non-Natural Rhodium Homologue of Coenzyme B-12

Widner, FJ; Lawrence, AD; Deery, E; Heldt, D; Frank, S; Gruber, K; Wurst, K; ... Kraeutler, B; + view all (2016) Total Synthesis, Structure, and Biological Activity of Adenosylrhodibalamin, the Non-Natural Rhodium Homologue of Coenzyme B-12. In: (Proceedings) 6th EuCheMS Chemistry Congress. (pp. pp. 11281-11286). WILEY-V C H VERLAG GMBH Green open access

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Abstract

B12 is unique among the vitamins as it is biosynthesized only by certain prokaryotes. The complexity of its synthesis relates to its distinctive cobalt corrin structure, which is essential for B12 biochemistry and renders coenzyme B12 (AdoCbl) so intriguingly suitable for enzymatic radical reactions. However, why is cobalt so fit for its role in B12-dependent enzymes? To address this question, we considered the substitution of cobalt in AdoCbl with rhodium to generate the rhodium analogue 5′-deoxy-5′-adenosylrhodibalamin (AdoRbl). AdoRbl was prepared by de novo total synthesis involving both biological and chemical steps. AdoRbl was found to be inactive in vivo in microbial bioassays for methionine synthase and acted as an in vitro inhibitor of an AdoCbl-dependent diol dehydratase. Solution NMR studies of AdoRbl revealed a structure similar to that of AdoCbl. However, the crystal structure of AdoRbl revealed a conspicuously better fit of the corrin ligand for RhIII than for CoIII, challenging the current views concerning the evolution of corrins.

Type: Proceedings paper
Title: Total Synthesis, Structure, and Biological Activity of Adenosylrhodibalamin, the Non-Natural Rhodium Homologue of Coenzyme B-12
Event: 6th EuCheMS Chemistry Congress
Location: Seville, SPAIN
Dates: 11 September 2016 - 15 September 2016
Open access status: An open access version is available from UCL Discovery
DOI: 10.1002/anie.201603738
Additional information: © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Keywords: Science & Technology, Physical Sciences, Chemistry, Multidisciplinary, Chemistry, biosynthesis, cobalt, total synthesis, transition metal, VitaminB(12), MOLECULAR-STRUCTURE, GENE-EXPRESSION, NUCLEIC-ACIDS, ADENOSYLCOBALAMIN, VITAMIN-B-12, BIOSYNTHESIS, COFACTORS, ENZYMES, ORIGIN, TETRAPYRROLES
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Biochemical Engineering
URI: https://discovery.ucl.ac.uk/id/eprint/1535445
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