Synthesis, spectral characterization and crystal structure of Chlororhodibalamin: A synthesis platform for rhodium analogues of vitamin B12 and for Rh-based antivitamins B12

Florian J. Widner; Christoph Kieninger; Klaus Wurst; Evelyne Deery; Andrew D. Lawrence; Martin J. Warren; Bernhard Kräutler

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

Florian J. Widner, Christoph Kieninger, Klaus Wurst, Evelyne Deery, Andrew D. Lawrence, Martin J. Warren, Bernhard Kräutler

Research output: Contribution to journal › Article › peer-review

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Abstract

Chlororhodibalamin (ClRhbl), a rhodium analogue of vitamin B₁₂(cyanocobalamin), was prepared in 84% yield by metalation of the metal-free B₁₂ligand hydrogenobalamin using the Rh^I-complex [Rh(CO)₂Cl]₂. ClRhbl was identified and characterized by UV/Vis, circular dichroism, high-resolution mass and heteronuclear NMR spectra. The Rh^III-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 Co^III-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.

Original language	English
Pages (from-to)	332-337
Number of pages	6
Journal	Synthesis-Stuttgart
Volume	53
Issue number	2
Early online date	5 Oct 2020
DOIs	https://doi.org/10.1055/s-0040-1707288
Publication status	Published - 19 Jan 2021

Keywords

antivitamin
inhibitors
metalation
natural products
porphyrins
rhodium
transition metals
vitamins

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title = "Synthesis, spectral characterization and crystal structure of Chlororhodibalamin: A synthesis platform for rhodium analogues of vitamin B12 and for Rh-based antivitamins B12",

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.",

keywords = "antivitamin, inhibitors, metalation, natural products, porphyrins, rhodium, transition metals, vitamins",

author = "Widner, {Florian J.} and Christoph Kieninger and Klaus Wurst and Evelyne Deery and Lawrence, {Andrew D.} and Warren, {Martin J.} and Bernhard Kr{\"a}utler",

note = "Funding Information: 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. ",

year = "2021",

month = jan,

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doi = "10.1055/s-0040-1707288",

language = "English",

volume = "53",

pages = "332--337",

journal = "Synthesis-Stuttgart",

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Synthesis, spectral characterization and crystal structure of Chlororhodibalamin: A synthesis platform for rhodium analogues of vitamin B12 and for Rh-based antivitamins B12. / Widner, Florian J.; Kieninger, Christoph; Wurst, Klaus et al.

In: Synthesis-Stuttgart, Vol. 53, No. 2, 19.01.2021, p. 332-337.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis, spectral characterization and crystal structure of Chlororhodibalamin: A synthesis platform for rhodium analogues of vitamin B12 and for Rh-based antivitamins B12

AU - Widner, Florian J.

AU - Kieninger, Christoph

AU - Wurst, Klaus

AU - Deery, Evelyne

AU - Lawrence, Andrew D.

AU - Warren, Martin J.

AU - Kräutler, Bernhard

N1 - Funding Information: 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.

PY - 2021/1/19

Y1 - 2021/1/19

N2 - 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.

AB - 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.

KW - antivitamin

KW - inhibitors

KW - metalation

KW - natural products

KW - porphyrins

KW - rhodium

KW - transition metals

KW - vitamins

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DO - 10.1055/s-0040-1707288

M3 - Article

AN - SCOPUS:85092704370

VL - 53

SP - 332

EP - 337

JO - Synthesis-Stuttgart

JF - Synthesis-Stuttgart

SN - 0039-7881

IS - 2

ER -

Synthesis, spectral characterization and crystal structure of Chlororhodibalamin: A synthesis platform for rhodium analogues of vitamin B12 and for Rh-based antivitamins B12

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