Iron catalyzed double bond isomerization: evidence for an FeI/FeIII catalytic cycle

Callum Woof; Derek J Durand; Natalie Fey; Emma Richards; Ruth Webster

doi:10.1002/chem.202004980

Iron catalyzed double bond isomerization: evidence for an Fe^I/Fe^III catalytic cycle

Callum Woof, Derek J Durand, Natalie Fey, Emma Richards, Ruth Webster

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Abstract

Iron‐catalyzed isomerization of alkenes is reported using an iron(II) β‐diketiminate pre‐catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre‐catalyst activation step that gives access to an η 2 ‐coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

Original language	English
Pages (from-to)	5972-5977
Number of pages	6
Journal	Chemistry - A European Journal
Volume	27
Issue number	19
Early online date	25 Jan 2021
DOIs	https://doi.org/10.1002/chem.202004980
Publication status	Published - 2 Apr 2021

Funding

The EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) is thanked for funding CRW and DJD. We thank the EPSRC UK National Mass Spectrometry Facility at Swansea University for MS analysis and the Centre for Computational Chemistry at the University of Bristol for providing access to computing resources. The authors would also like to thank Dr. Josh Tibbetts for assistance with ozonolysis experiments, Professor Frank Marken and Mr. Jack Stewart for helpful discussion on Cyclic Voltammetry studies, and Dr. Danila Gasperini for the preparation of the FeI ?6-toluene analogue of 1A.

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10.1002/chem.202004980Licence: CC BY

EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds
Webster, R. (PI)
Engineering and Physical Sciences Research Council
3/12/17 → 2/03/24
Project: Research council

Cite this

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title = "Iron catalyzed double bond isomerization: evidence for an FeI/FeIII catalytic cycle",

abstract = "Iron‐catalyzed isomerization of alkenes is reported using an iron(II) β‐diketiminate pre‐catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre‐catalyst activation step that gives access to an η 2 ‐coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.",

author = "Callum Woof and Durand, {Derek J} and Natalie Fey and Emma Richards and Ruth Webster",

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T1 - Iron catalyzed double bond isomerization: evidence for an FeI/FeIII catalytic cycle

AU - Woof, Callum

AU - Durand, Derek J

AU - Fey, Natalie

AU - Richards, Emma

AU - Webster, Ruth

PY - 2021/4/2

Y1 - 2021/4/2

N2 - Iron‐catalyzed isomerization of alkenes is reported using an iron(II) β‐diketiminate pre‐catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre‐catalyst activation step that gives access to an η 2 ‐coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

AB - Iron‐catalyzed isomerization of alkenes is reported using an iron(II) β‐diketiminate pre‐catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre‐catalyst activation step that gives access to an η 2 ‐coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

U2 - 10.1002/chem.202004980

DO - 10.1002/chem.202004980

M3 - Article

SN - 0947-6539

VL - 27

SP - 5972

EP - 5977

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 19

ER -

Iron catalyzed double bond isomerization: evidence for an FeI/FeIII catalytic cycle

Abstract

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EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds

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Iron catalyzed double bond isomerization: evidence for an Fe^I/Fe^III catalytic cycle