Defluoroalkylation of trifluoromethane with organolithium reagents: mechanism and synthesis of fluoroalkenes
Author(s)
Warsame, Hodan R
Patrick, Sarah L
Bull, James A
Miller, Philip W
Crimmin, Mark R
Type
Journal Article
Abstract
Trifluoromethane (HCF3, HFC-23) is a byproduct of fluoropolymer production that has limited applications. It is often stored or destroyed at the point of production, but if released into the environment is a potent greenhouse gas with a global warming potential of 14 600 times that of CO2. State-of-the-art chemical technologies for upgrading HCF3 typically occur with conservation of the CF3 group. These approaches will come under increased scrutiny as concern over the environmental impact of perfluoroalkyl substances (PFAS) continues to grow. A more sustainable approach involves synthetic transformations that repurpose the atomic content of HCF3 while also destroying the CF3 group. In this paper, we report a rare example of the transformation of HCF3 into a fluoroalkene functional group through defluoroalkylation. We rationalise product formation through DFT calculations, scale-up the synthesis through continuous flow methods, and show that a fluoroalkene reagent derived from HCF3 is a competent nucleophile for the fluoroethenylation of a range of aldehydes.
Date Issued
2026-01-02
Date Acceptance
2025-10-28
Citation
Angewandte Chemie International Edition, 2026, 65 (1)
ISSN
1433-7851
Publisher
Wiley
Journal / Book Title
Angewandte Chemie International Edition
Volume
65
Issue
1
Copyright Statement
© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
License URL
Identifier
10.1002/anie.202516598
Subjects
ACTIVATION
BUILDING-BLOCKS
C-F activation
Chemistry
Chemistry, Multidisciplinary
COMPLEXES
Defluoroalkylation
DIFLUOROCARBENE
DIFLUOROMETHYLATION
Fluoroalkene
FLUOROFORM
FUNCTIONALIZED 1,1-DIFLUORO-1-ALKENES
GENERALIZED GRADIENT APPROXIMATION
Organolithium
Physical Sciences
RAY CRYSTAL-STRUCTURE
Science & Technology
Trifluoromethane
X-RAY
Publication Status
Published
Article Number
e16598
Date Publish Online
2025-11-06