Quantitative prediction of selectivity in iridium-catalysed hydrogen isotope exchange reactions

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

doi:10.26434/chemrxiv.12589529

Quantitative prediction of 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: Other contribution

2 Downloads (Pure)

Abstract

A pallette 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 constructred 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
Type	Preprint
Media of output	PDF
Number of pages	6
Place of Publication	[London]
DOIs	https://doi.org/10.26434/chemrxiv.12589529
Publication status	Published - 2 Jul 2020

Keywords

isotopic labelling
iridium catalysis
reaction selectivity
C-H activation

Access to Document

10.26434/chemrxiv.12589529Licence: CC BY-NC-ND 4.0

Timofeeva-etal-2020-Quantitative-prediction-of-selectivity-in-iridium-catalysed-hydrogen-isotope-exchange-reactionsSubmitted manuscript, 1.26 MBLicence: CC BY-NC-ND 4.0
Timofeeva-etal-2020-Quantitative-prediction-of-selectivity-in-iridium-catalysed-hydrogen-isotope-exchange-reactions-suppl-infoSubmitted manuscript, 20.6 MBLicence: CC BY-NC-ND 4.0

Fingerprint Dive into the research topics of 'Quantitative prediction of selectivity in iridium-catalysed hydrogen isotope exchange reactions'. Together they form a unique fingerprint.

Projects

1 Active

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

Nelson, D. & Kerr, W.

Leverhulme Trust

1/10/18 → 30/09/21

Project: Research

Datasets

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 Sep 2020

DOI: 10.15129/46bc02ea-f605-44f5-978c-fd7852fbdc19

Dataset

Cite this

Timofeeva, D. S., Lindsay, D. M., Kerr, W. J., & Nelson, D. J. (2020, Jul 2). Quantitative prediction of selectivity in iridium-catalysed hydrogen isotope exchange reactions. https://doi.org/10.26434/chemrxiv.12589529

@misc{4dd8ae75e44f4a6c8e4ea9d6df9b59cb,

title = "Quantitative prediction of selectivity in iridium-catalysed hydrogen isotope exchange reactions",

abstract = "A pallette 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 constructred 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 = "isotopic labelling, iridium catalysis, reaction selectivity, C-H activation",

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

year = "2020",

month = jul,

day = "2",

doi = "10.26434/chemrxiv.12589529",

language = "English",

type = "Other",

}

TY - GEN

T1 - Quantitative prediction of selectivity in iridium-catalysed hydrogen isotope exchange reactions

AU - Timofeeva, Daria S.

AU - Lindsay, David M.

AU - Kerr, William J.

AU - Nelson, David J.

PY - 2020/7/2

Y1 - 2020/7/2

N2 - A pallette 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 constructred 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 pallette 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 constructred 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 - isotopic labelling

KW - iridium catalysis

KW - reaction selectivity

KW - C-H activation

U2 - 10.26434/chemrxiv.12589529

DO - 10.26434/chemrxiv.12589529

M3 - Other contribution

CY - [London]

ER -