Highly active iridium(i) complexes for the selective hydrogenation of carbon–carbon multiple bonds

Bennie, Linsey S.; Fraser, C. J. W.; Irvine, S. Rodman; Kerr, William J.; Andersson, Shalini; Nilsson, Göran N.

doi:10.1039/c1cc14367k

Cited by 34 publications

(22 citation statements)

References 13 publications

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“…[9] Througho ur on-goings tudies, we have now established that non-aromatic unsaturated moieties containing as uitable donor group can also undergo selectiveC ÀHa ctivationa nd hydrogen-isotopee xchange (Scheme 1).…”

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confidence: 98%

Iridium(I) N‐Heterocyclic Carbene (NHC)/Phosphine Catalysts for Mild and Chemoselective Hydrogenation Processes

Kerr

Mudd

Brown

2016

Chemistry A European J

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confidence: 98%

Iridium(I) N‐Heterocyclic Carbene (NHC)/Phosphine Catalysts for Mild and Chemoselective Hydrogenation Processes

Kerr

Mudd

Brown

2016

Chemistry A European J

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“…[12] In this regard, we have reported on the preparation and application of a series of new iridium complexes bearing a bulky Nheterocyclic carbene (NHC), 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), alongside an appreciably encumbered phosphine, and which have appreciable potential as highly active catalysts for HIE with deuterium. [13] Additionally, we have shown that these robust and practically accessible iridium species can be applied within the selective reduction of alkenes (and alkynes) [14] and in the Zselective dimerization of terminal alkynes. [15] Herein, we report the activity and selectivity spectrum of this class of iridium complex in the area of deuterium and, importantly, tritium labelling, as well as our initial investigations into the overall mechanism of the hydrogen isotope exchange process with these emerging catalyst species.…”

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confidence: 99%

The Synthesis of Highly Active Iridium(I) Complexes and their Application in Catalytic Hydrogen Isotope Exchange

et al. 2014

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This version is available at https://strathprints.strath.ac.uk/49161/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Abstract. : A series of robust iridium(I) complexes bearing a sterically encumbered N-heterocyclic carbene ligand, alongside a phosphine ligand, has been synthesised and investigated in hydrogen isotope exchange processes. These complexes have allowed isotope incorporation over a range of substrates with the use of practically convenient deuterium and tritium gas. Moreover, these active catalysts are capable of isotope incorporation to particularly high levels, whilst employing low catalyst loadings and in short reaction times. In addition to this, these new catalyst species have shown flexible levels of chemoselectivity, which can be altered by simple manipulation of preparative approaches.Furthermore, a number of industrially-relevant drug molecules have also been labelled, including the sulfonamide containing drug, Celecoxib. Alongside detailed NMR experiments, initial mechanistic investigations have also been performed, providing insight into both substrate binding energies, and, more importantly, relative energies of key steps in the mechanistic cycle as part of the overall exchange process.

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“…8 In relation to this, studies by Nolan et al have divulged that iridium species with the alternative specific combination of a bulky Nheterocyclic carbene (NHC) and a pyridine ligand represent appreciably robust complexes that are active within both alkene hydrogenation 9 and transfer hydrogenation protocols. 10 In view of these findings, and based on the knowledge that judicious and careful manipulation of the ligands supporting the iridium centre is critical for success within hydrogen isotope exchange processes, we turned our attention to the application of the general class of Ir(NHC)(py) complexes Our initial investigations involved the preparation of catalysts 3a-c 9,10 via the modified preparative procedure shown in Table 1.…”

Section: Scheme 1 Hydrogen Isotope Exchange Processmentioning

confidence: 99%

Isotopic Labelling of Functionalised Arenes Catalysed by Iridium(I) Species of the [(cod)Ir(NHC)(py)]PF6 Complex Class

Kerr

Paterson

Herbert

et al. 2015

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0035-1560518This version is available at https://strathprints.strath.ac.uk/54692/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Strathprints administrator: strathprints@strath.ac.ukThe Strathprints institutional repository (https://strathprints.strath.ac.uk) is a digital archive of University of Strathclyde research outputs. It has been developed to disseminate open access research outputs, expose data about those outputs, and enable the management and persistent access to Strathclyde's intellectual output. Abstract Ir(I) complexes of the type [(COD)Ir(NHC)(Py)]PF6 have been exposed as efficient catalysts in the area of hydrogen isotope exchange. More specifically, via an ortho-directed C-H activation process, high levels of deuterium incorporation have been achieved using low levels of catalyst over a range of functionalised aromatic compounds. Additionally, the developed protocol has been extended to include a selected pharmacological target, where chemoselective labelling is observed within such a multifunctional substrate. Key words iridium, C-H activation, hydrogen isotope exchange, deuterationIsotopic labelling with heavy hydrogen isotopes (D2 and T2) is widely used as a means to monitor the biological fate of a potential drug molecule. 2 In relation to this, methods that deliver hydrogen isotope exchange (HIE) are of appreciable importance in accessing such isotopically-labelled species, whilst also being central to the provision of analogous deuterated compounds for use as internal standards as aligned with mass spectrometry, 3 for kinetic isotope studies, 4 and for the alteration of reaction pathways in total synthesis. 5 As such, direct, flexible, and selective means of introducing hydrogen isotopes continues to be the focus of considerable research attention. In this regard, studies from our laboratory have shown that a range of iridium complexes of the type [(COD)Ir(IMes)(PR3)]X are very effective homogeneous catalysts which mediate the exchange of hydrogen with deuterium (or tritium) via an ortho-directed C-H activation process. 2c,6 The key to their applicability in this area lies with the ability of such complexes to selectively target unactivated C-H bonds, whilst simultaneously allowing convenient isotope incorporation with the use of, practically convenient, deuterium or tritium gas (Sc...

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Highly active iridium(i) complexes for the selective hydrogenation of carbon–carbon multiple bonds

Cited by 34 publications

References 13 publications

Iridium(I) N‐Heterocyclic Carbene (NHC)/Phosphine Catalysts for Mild and Chemoselective Hydrogenation Processes

Iridium(I) N‐Heterocyclic Carbene (NHC)/Phosphine Catalysts for Mild and Chemoselective Hydrogenation Processes

The Synthesis of Highly Active Iridium(I) Complexes and their Application in Catalytic Hydrogen Isotope Exchange

Isotopic Labelling of Functionalised Arenes Catalysed by Iridium(I) Species of the [(cod)Ir(NHC)(py)]PF6 Complex Class

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