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α- and β-Eliminations in Transition Metal Complexes : Strategies to Cleave Unstrained C−C and C−F Bonds

Karimzadeh-Younjali, Morteza LU and Wendt, Ola F. LU (2021) In Helvetica Chimica Acta 104(11).
Abstract

Oxidative addition is the standard process for single-bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ-bonds e. g. C(sp3)−F and C(sp3)−C(sp3) bonds are the exceptions in this respect. This short review aims at demonstrating how both α- and β-eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α- and β-eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β-eliminations is controlled by the... (More)

Oxidative addition is the standard process for single-bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ-bonds e. g. C(sp3)−F and C(sp3)−C(sp3) bonds are the exceptions in this respect. This short review aims at demonstrating how both α- and β-eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α- and β-eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β-eliminations is controlled by the s-character of the participating bonds where a higher s-character gives a better overlap in the multi-center transition state thereby increasing the reactivity; still β-aryl eliminations can compete with the classical β-hydrogen eliminations in certain cases.

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Please use this url to cite or link to this publication:
author
and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
cleavage reactions, elimination, insertion, transition metals, unstrained
in
Helvetica Chimica Acta
volume
104
issue
11
publisher
John Wiley & Sons Inc.
external identifiers
  • scopus:85117224321
ISSN
0018-019X
DOI
10.1002/hlca.202100114
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2021 The Authors. Helvetica Chimica Acta published by Wiley-VHCA AG, Zurich, Switzerland
id
9afe88b6-ac85-4f62-a90a-504a7f06154b
date added to LUP
2021-11-05 15:11:41
date last changed
2022-04-19 17:44:34
@article{9afe88b6-ac85-4f62-a90a-504a7f06154b,
  abstract     = {{<p>Oxidative addition is the standard process for single-bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ-bonds e. g. C(sp<sup>3</sup>)−F and C(sp<sup>3</sup>)−C(sp<sup>3</sup>) bonds are the exceptions in this respect. This short review aims at demonstrating how both α- and β-eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α- and β-eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β-eliminations is controlled by the s-character of the participating bonds where a higher s-character gives a better overlap in the multi-center transition state thereby increasing the reactivity; still β-aryl eliminations can compete with the classical β-hydrogen eliminations in certain cases.</p>}},
  author       = {{Karimzadeh-Younjali, Morteza and Wendt, Ola F.}},
  issn         = {{0018-019X}},
  keywords     = {{cleavage reactions; elimination; insertion; transition metals; unstrained}},
  language     = {{eng}},
  number       = {{11}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Helvetica Chimica Acta}},
  title        = {{α- and β-Eliminations in Transition Metal Complexes : Strategies to Cleave Unstrained C−C and C−F Bonds}},
  url          = {{http://dx.doi.org/10.1002/hlca.202100114}},
  doi          = {{10.1002/hlca.202100114}},
  volume       = {{104}},
  year         = {{2021}},
}