A quantitative empirical directing group scale for selectivity in iridium-catalysed hydrogen isotope exchange reactions

Daria S. Timofeeva; David M. Lindsay; William J. Kerr; David J. Nelson

doi:10.1039/D0CY01597K

A quantitative empirical directing group scale for selectivity in iridium-catalysed hydrogen isotope exchange reactions

Daria S. Timofeeva, David M. Lindsay, William J. Kerr, David J. Nelson

Pure And Applied Chemistry

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

8 Citations (Scopus)

13 Downloads (Pure)

Abstract

A palette of commonly used directing groups, including various pharmaceutically relevant nitrogen-containing heterocycles, are quantitatively ranked based on the results of intermolecular hydrogen isotope exchange competition reactions using two iridium complexes: [Ir(COD)(IMes)(PPh3)][BArF24] and [IrCl(COD)(IMes)]. The directing group power scales that have been constructed from these data reveal a wide range of reactivity covering four orders of magnitude. Intramolecular competition experiments have demonstrated that the obtained reactivity scale provides accurate predictions of regioselectivity within molecules with multiple competing directing groups. This work contributes to our understanding and control of regioselectivity in metal-catalysed C-H activation reactions.

Original language	English
Pages (from-to)	7249-7255
Number of pages	7
Journal	Catalysis Science and Technology
Volume	10
Issue number	21
Early online date	4 Sept 2020
DOIs	https://doi.org/10.1039/D0CY01597K
Publication status	Published - 7 Nov 2020

Keywords

heterocycles
hydrogen isotope exchange
iridium complexes

Access to Document

10.1039/D0CY01597KLicence: CC BY 3.0

Timofeeva-etal-CST-2020-A-quantitative-empirical-directing-group-scale-for-selectivityFinal published version, 3.03 MBLicence: CC BY 3.0

David Nelson, MChem PhD PGDip FRSC FHEA
- david.nelsonstrath.acuk
- Pure And Applied Chemistry - Senior Lecturer
Person: Academic

1 Finished

Defining, Quantifying, and Understanding Selectivity Paradigms in Iridium-Cataly
Nelson, D. & Kerr, W.
Leverhulme Trust
1/10/18 → 31/12/22
Project: Research

Data for: "A quantitative empirical directing group scale for selectivity in iridium-catalysed hydrogen isotope exchange reactions"
Timofeeva, D. (Creator), Lindsay, D. (Creator), Kerr, W. (Creator) & Nelson, D. (Creator), University of Strathclyde, 7 Sept 2020
DOI: 10.15129/46bc02ea-f605-44f5-978c-fd7852fbdc19
Dataset

AVIII400 NMR Spectrometer with Cryoprobe
John Parkinson
Pure And Applied Chemistry
Facility/equipment: Equipment

8 Citations
2 Article

Are rate and selectivity correlated in iridium-catalysed hydrogen isotope exchange reactions?
Timofeeva, D. S., Lindsay, D. M., Kerr, W. J. & Nelson, D. J., 21 Aug 2021, In: Catalysis Science and Technology. 11, 16, p. 5498-5504 7 p.
Research output: Contribution to journal › Article › peer-review

Open Access
File
1 Citation (Scopus)

12 Downloads (Pure)
Insights into mechanism and selectivity in ruthenium(II)-catalysed ortho-arylation reactions directed by Lewis basic groups
McIntyre, J., Mayoral-Soler, I., Salvador Sedano, P., Poater, A. & Nelson, D. J., 1 Jun 2018, (E-pub ahead of print) In: Catalysis Science and Technology.
Research output: Contribution to journal › Article › peer-review

Open Access
File
20 Citations (Scopus)

14 Downloads (Pure)

Cite this

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title = "A quantitative empirical directing group scale for selectivity in iridium-catalysed hydrogen isotope exchange reactions",

abstract = "A palette of commonly used directing groups, including various pharmaceutically relevant nitrogen-containing heterocycles, are quantitatively ranked based on the results of intermolecular hydrogen isotope exchange competition reactions using two iridium complexes: [Ir(COD)(IMes)(PPh3)][BArF24] and [IrCl(COD)(IMes)]. The directing group power scales that have been constructed from these data reveal a wide range of reactivity covering four orders of magnitude. Intramolecular competition experiments have demonstrated that the obtained reactivity scale provides accurate predictions of regioselectivity within molecules with multiple competing directing groups. This work contributes to our understanding and control of regioselectivity in metal-catalysed C-H activation reactions.",

keywords = "heterocycles, hydrogen isotope exchange, iridium complexes",

author = "Timofeeva, {Daria S.} and Lindsay, {David M.} and Kerr, {William J.} and Nelson, {David J.}",

year = "2020",

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day = "7",

doi = "10.1039/D0CY01597K",

language = "English",

volume = "10",

pages = "7249--7255",

journal = "Catalysis Science and Technology",

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publisher = "Royal Society of Chemistry",

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AU - Timofeeva, Daria S.

AU - Lindsay, David M.

AU - Kerr, William J.

AU - Nelson, David J.

PY - 2020/11/7

Y1 - 2020/11/7

N2 - A palette of commonly used directing groups, including various pharmaceutically relevant nitrogen-containing heterocycles, are quantitatively ranked based on the results of intermolecular hydrogen isotope exchange competition reactions using two iridium complexes: [Ir(COD)(IMes)(PPh3)][BArF24] and [IrCl(COD)(IMes)]. The directing group power scales that have been constructed from these data reveal a wide range of reactivity covering four orders of magnitude. Intramolecular competition experiments have demonstrated that the obtained reactivity scale provides accurate predictions of regioselectivity within molecules with multiple competing directing groups. This work contributes to our understanding and control of regioselectivity in metal-catalysed C-H activation reactions.

AB - A palette of commonly used directing groups, including various pharmaceutically relevant nitrogen-containing heterocycles, are quantitatively ranked based on the results of intermolecular hydrogen isotope exchange competition reactions using two iridium complexes: [Ir(COD)(IMes)(PPh3)][BArF24] and [IrCl(COD)(IMes)]. The directing group power scales that have been constructed from these data reveal a wide range of reactivity covering four orders of magnitude. Intramolecular competition experiments have demonstrated that the obtained reactivity scale provides accurate predictions of regioselectivity within molecules with multiple competing directing groups. This work contributes to our understanding and control of regioselectivity in metal-catalysed C-H activation reactions.

KW - heterocycles

KW - hydrogen isotope exchange

KW - iridium complexes

U2 - 10.1039/D0CY01597K

DO - 10.1039/D0CY01597K

M3 - Article

SN - 2044-4753

VL - 10

SP - 7249

EP - 7255

JO - Catalysis Science and Technology

JF - Catalysis Science and Technology

IS - 21

ER -

A quantitative empirical directing group scale for selectivity in iridium-catalysed hydrogen isotope exchange reactions

Abstract

Keywords

Access to Document

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Profiles

David Nelson, MChem PhD PGDip FRSC FHEA

Projects

Defining, Quantifying, and Understanding Selectivity Paradigms in Iridium-Cataly

Datasets

Data for: "A quantitative empirical directing group scale for selectivity in iridium-catalysed hydrogen isotope exchange reactions"

Equipment

AVIII400 NMR Spectrometer with Cryoprobe

Research output

Are rate and selectivity correlated in iridium-catalysed hydrogen isotope exchange reactions?

Insights into mechanism and selectivity in ruthenium(II)-catalysed ortho-arylation reactions directed by Lewis basic groups

Cite this