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

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
• Public URL: https://durham-repository.worktribe.com/output/1313352