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C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions
An assessment of the C−H activation catalyst [(COD)Ir(IMes)(PPh(3))]PF(6) (COD=1,5‐cyclooctadiene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear ord...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7232431/ https://www.ncbi.nlm.nih.gov/pubmed/31917506 http://dx.doi.org/10.1002/anie.201914220 |
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author | Valero, Mégane Kruissink, Thomas Blass, Jennifer Weck, Remo Güssregen, Stefan Plowright, Alleyn T. Derdau, Volker |
author_facet | Valero, Mégane Kruissink, Thomas Blass, Jennifer Weck, Remo Güssregen, Stefan Plowright, Alleyn T. Derdau, Volker |
author_sort | Valero, Mégane |
collection | PubMed |
description | An assessment of the C−H activation catalyst [(COD)Ir(IMes)(PPh(3))]PF(6) (COD=1,5‐cyclooctadiene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear order of the directing groups in the hydrogen isotope exchange (HIE) with an iridium (I) catalyst. Through DFT calculations the iridium–substrate coordination complex has been identified to be the main trigger for reactivity and selectivity in the competition situation with two or more directing groups. We postulate that the competition concept found in this HIE reaction can be used to explain regioselectivities in other transition‐metal‐catalyzed functionalization reactions of complex drug‐type molecules as long as a C−H activation mechanism is involved. |
format | Online Article Text |
id | pubmed-7232431 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-72324312020-05-19 C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions Valero, Mégane Kruissink, Thomas Blass, Jennifer Weck, Remo Güssregen, Stefan Plowright, Alleyn T. Derdau, Volker Angew Chem Int Ed Engl Communications An assessment of the C−H activation catalyst [(COD)Ir(IMes)(PPh(3))]PF(6) (COD=1,5‐cyclooctadiene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear order of the directing groups in the hydrogen isotope exchange (HIE) with an iridium (I) catalyst. Through DFT calculations the iridium–substrate coordination complex has been identified to be the main trigger for reactivity and selectivity in the competition situation with two or more directing groups. We postulate that the competition concept found in this HIE reaction can be used to explain regioselectivities in other transition‐metal‐catalyzed functionalization reactions of complex drug‐type molecules as long as a C−H activation mechanism is involved. John Wiley and Sons Inc. 2020-02-03 2020-03-27 /pmc/articles/PMC7232431/ /pubmed/31917506 http://dx.doi.org/10.1002/anie.201914220 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
spellingShingle | Communications Valero, Mégane Kruissink, Thomas Blass, Jennifer Weck, Remo Güssregen, Stefan Plowright, Alleyn T. Derdau, Volker C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions |
title | C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions |
title_full | C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions |
title_fullStr | C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions |
title_full_unstemmed | C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions |
title_short | C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions |
title_sort | c−h functionalization—prediction of selectivity in iridium(i)‐catalyzed hydrogen isotope exchange competition reactions |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7232431/ https://www.ncbi.nlm.nih.gov/pubmed/31917506 http://dx.doi.org/10.1002/anie.201914220 |
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