2,3,3,3-Tetrafluoropropene (HFO-1234yf) as a CF3-building block: synthesis of enol ethers and vinyl sulfides

Murray, Ben James; Ball, Ellis David; Harsanyi, Antal; Sandford, Graham

doi:10.1002/ejoc.201901445

2,3,3,3-Tetrafluoropropene (HFO-1234yf) as a CF3-building block: synthesis of enol ethers and vinyl sulfides

Murray, Ben James; Ball, Ellis David; Harsanyi, Antal; Sandford, Graham

Authors

Ben James Murray

Ellis David Ball

Antal Harsanyi

Graham Sandford

Abstract

2,3,3,3‐Tetrafluoropropene (HFO‐1234yf) is an inexpensive and readily available fluorinated building block, owing to its growing use as a low global warming potential 4th generation refrigerant, but there have so far been few reported uses of this fluoroalkene in organic synthesis. Here we report our investigations into nucleophilic substitution reactions of HFO‐1234yf with alkoxide and thiolate derivatives. The regiochemistry of these transformations varies with conditions and we propose these reactions proceed via addition‐elimination with reversible formation of a carbanion intermediate. The regioselectivity is dictated by hard/soft nucleophile/electrophile control. This is supported by deuterium trapping of the proposed reactive intermediate. The effect of solvent and base choice was examined and the substrate scope for the synthesis of α‐trifluoromethyl enol ethers was expanded.

Citation

Murray, B. J., Ball, E. D., Harsanyi, A., & Sandford, G. (2019). 2,3,3,3-Tetrafluoropropene (HFO-1234yf) as a CF3-building block: synthesis of enol ethers and vinyl sulfides. European Journal of Organic Chemistry, 2019(47), 7666-7672. https://doi.org/10.1002/ejoc.201901445

Journal Article Type	Article
Acceptance Date	Nov 20, 2019
Online Publication Date	Dec 10, 2019
Publication Date	Dec 19, 2019
Deposit Date	Nov 21, 2019
Publicly Available Date	Dec 10, 2020
Journal	European Journal of Organic Chemistry
Print ISSN	1434-193X
Electronic ISSN	1099-0690
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	2019
Issue	47
Pages	7666-7672
DOI	https://doi.org/10.1002/ejoc.201901445

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Copyright Statement
This is the accepted version of the following article: Murray, Ben James, Ball, Ellis David, Harsanyi, Antal & Sandford, Graham (2019). 2,3,3,3-Tetrafluoropropene (HFO-1234yf) as a CF3-building block: synthesis of enol ethers and vinyl sulfides. European Journal of Organic Chemistry 2019(47): 7666-7672 which has been published in final form at https://doi.org/10.1002/ejoc.201901445. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for self-archiving.