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DOI: 10.1055/s-0040-1707288
Synthesis, Spectral Characterization and Crystal Structure of Chlororhodibalamin: A Synthesis Platform for Rhodium Analogues of Vitamin B12 and for Rh-Based Antivitamins B12
Funding by the Austrian Science Fund (FWF, projects No. P-28892 and P-30359 to BK), as well as by the Biotechnology and Biological Sciences Research Council (BBSRC, grant number BB/S002197/1 to MJW) and Royal Society (INF\R2\180062 to MJW) is gratefully acknowledged.
Abstract
Chlororhodibalamin (ClRhbl), a rhodium analogue of vitamin B12 (cyanocobalamin), was prepared in 84% yield by metalation of the metal-free B12 ligand hydrogenobalamin using the RhI-complex [Rh(CO)2Cl]2. ClRhbl was identified and characterized by UV/Vis, circular dichroism, high-resolution mass and heteronuclear NMR spectra. The RhIII-corrin ClRhbl features the ‘base-on’ architecture of vitamin B12. X-ray analysis of single crystals of ClRhbl have revealed its detailed 3D-geometry and close structural similarity to the CoIII-analogue chlorocobalamin (ClCbl). ClRhbl is a versatile starting material for the preparation of other rhodibalamins, among them the organometallic derivatives adenosylrhodibalamin and methylrhodibalamin, the Rh analogues of the important coenzyme and cofactor forms of B12, adenosylcobalamin and methylcobalamin.
Key words
rhodium - transition metals - vitamins - porphyrins - natural products - antivitamin - metalation - inhibitorsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707288.
- Supporting Information
Publication History
Received: 26 July 2020
Accepted after revision: 27 August 2020
Article published online:
05 October 2020
© 2021. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)
Georg Thieme Verlag KG
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- 1b Present address: Formycon AG, Fraunhoferstraße 15, 82152 Martinsried/Planegg, Germany
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