Direct electrochemical hydrodefluorination of trifluoromethylketones enabled by non-protic conditions

John R Box; Alex Atkins; Alastair J J Lennox

doi:10.1039/d1sc01574e

Direct electrochemical hydrodefluorination of trifluoromethylketones enabled by non-protic conditions

John R Box, Alex Atkins, Alastair J J Lennox^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

45 Citations (Scopus)

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Abstract

CF2H groups are unique due to the combination of their lipophilic and hydrogen bonding properties. The strength of H-bonding is determined by the group to which it is appended. Several functional groups have been explored in this context including O, S, SO and SO2 to tune the intermolecular interaction. Difluoromethyl ketones are under-studied in this context, without a broadly accessible method for their preparation. Herein, we describe the development of an electrochemical hydrodefluorination of readily accessible trifluoromethylketones. The single-step reaction at deeply reductive potentials is uniquely amenable to challenging electron-rich substrates and reductively sensitive functionality. Key to this success is the use of non-protic conditions enabled by an ammonium salt that serves as a reductively stable, masked proton source. Analysis of their H-bonding has revealed difluoromethyl ketones to be potentially highly useful dual H-bond donor/acceptor moieties.

Original language	English
Pages (from-to)	10252-10258
Number of pages	7
Journal	Chemical Science
Volume	12
Issue number	30
Early online date	6 Jul 2021
DOIs	https://doi.org/10.1039/d1sc01574e
Publication status	Published - 14 Aug 2021

Bibliographical note

Funding Information:
We would like to thank the Royal Society (University Research Fellowship, Enhancement award and Research Grant for Research Fellow to AJJL), EPSRC (EP/S018050/1) and Syngenta for funding. We would also like to acknowledge Dr Natalie Pridmore (University of Bristol) for the X-ray crystallography. We would like to dedicate this manuscript to Prof Shannon Stahl on the occasion of his 50thbirthday.

Funding Information:
We would like to thank the Royal Society (University Research Fellowship, Enhancement award and Research Grant for Research Fellow to AJJL), EPSRC (EP/S018050/1) and Syngenta for funding. We would also like to acknowledge Dr Natalie Pridmore (University of Bristol) for the X-ray crystallography.

Publisher Copyright:
© The Royal Society of Chemistry 2021.

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Electrochemical hydrodefluorination of trifluoromethyl groups
Box, J. R. (Author), Lennox, A. (Supervisor) & Butts, C. P. (Supervisor), 9 May 2023
Student thesis: Doctoral Thesis › Doctor of Philosophy (PhD)

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title = "Direct electrochemical hydrodefluorination of trifluoromethylketones enabled by non-protic conditions",

abstract = "CF2H groups are unique due to the combination of their lipophilic and hydrogen bonding properties. The strength of H-bonding is determined by the group to which it is appended. Several functional groups have been explored in this context including O, S, SO and SO2 to tune the intermolecular interaction. Difluoromethyl ketones are under-studied in this context, without a broadly accessible method for their preparation. Herein, we describe the development of an electrochemical hydrodefluorination of readily accessible trifluoromethylketones. The single-step reaction at deeply reductive potentials is uniquely amenable to challenging electron-rich substrates and reductively sensitive functionality. Key to this success is the use of non-protic conditions enabled by an ammonium salt that serves as a reductively stable, masked proton source. Analysis of their H-bonding has revealed difluoromethyl ketones to be potentially highly useful dual H-bond donor/acceptor moieties.",

author = "Box, {John R} and Alex Atkins and Lennox, {Alastair J J}",

note = "Funding Information: We would like to thank the Royal Society (University Research Fellowship, Enhancement award and Research Grant for Research Fellow to AJJL), EPSRC (EP/S018050/1) and Syngenta for funding. We would also like to acknowledge Dr Natalie Pridmore (University of Bristol) for the X-ray crystallography. We would like to dedicate this manuscript to Prof Shannon Stahl on the occasion of his 50thbirthday. Funding Information: We would like to thank the Royal Society (University Research Fellowship, Enhancement award and Research Grant for Research Fellow to AJJL), EPSRC (EP/S018050/1) and Syngenta for funding. We would also like to acknowledge Dr Natalie Pridmore (University of Bristol) for the X-ray crystallography. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2021.",

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AU - Box, John R

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N1 - Funding Information: We would like to thank the Royal Society (University Research Fellowship, Enhancement award and Research Grant for Research Fellow to AJJL), EPSRC (EP/S018050/1) and Syngenta for funding. We would also like to acknowledge Dr Natalie Pridmore (University of Bristol) for the X-ray crystallography. We would like to dedicate this manuscript to Prof Shannon Stahl on the occasion of his 50thbirthday. Funding Information: We would like to thank the Royal Society (University Research Fellowship, Enhancement award and Research Grant for Research Fellow to AJJL), EPSRC (EP/S018050/1) and Syngenta for funding. We would also like to acknowledge Dr Natalie Pridmore (University of Bristol) for the X-ray crystallography. Publisher Copyright: © The Royal Society of Chemistry 2021.

PY - 2021/8/14

Y1 - 2021/8/14

N2 - CF2H groups are unique due to the combination of their lipophilic and hydrogen bonding properties. The strength of H-bonding is determined by the group to which it is appended. Several functional groups have been explored in this context including O, S, SO and SO2 to tune the intermolecular interaction. Difluoromethyl ketones are under-studied in this context, without a broadly accessible method for their preparation. Herein, we describe the development of an electrochemical hydrodefluorination of readily accessible trifluoromethylketones. The single-step reaction at deeply reductive potentials is uniquely amenable to challenging electron-rich substrates and reductively sensitive functionality. Key to this success is the use of non-protic conditions enabled by an ammonium salt that serves as a reductively stable, masked proton source. Analysis of their H-bonding has revealed difluoromethyl ketones to be potentially highly useful dual H-bond donor/acceptor moieties.

AB - CF2H groups are unique due to the combination of their lipophilic and hydrogen bonding properties. The strength of H-bonding is determined by the group to which it is appended. Several functional groups have been explored in this context including O, S, SO and SO2 to tune the intermolecular interaction. Difluoromethyl ketones are under-studied in this context, without a broadly accessible method for their preparation. Herein, we describe the development of an electrochemical hydrodefluorination of readily accessible trifluoromethylketones. The single-step reaction at deeply reductive potentials is uniquely amenable to challenging electron-rich substrates and reductively sensitive functionality. Key to this success is the use of non-protic conditions enabled by an ammonium salt that serves as a reductively stable, masked proton source. Analysis of their H-bonding has revealed difluoromethyl ketones to be potentially highly useful dual H-bond donor/acceptor moieties.

U2 - 10.1039/d1sc01574e

DO - 10.1039/d1sc01574e

M3 - Article (Academic Journal)

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VL - 12

SP - 10252

EP - 10258

JO - Chemical Science

JF - Chemical Science

IS - 30

ER -

Direct electrochemical hydrodefluorination of trifluoromethylketones enabled by non-protic conditions

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Electrochemical hydrodefluorination of trifluoromethyl groups

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