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2,3,3,3‐Tetrafluoropropene (HFO‐1234yf) as a CF 3 ‐Building Block: Synthesis of Enol Ethers and Vinyl Sulfides
Author(s) -
Murray Ben J.,
Ball Ellis D.,
Harsanyi Antal,
Sandford Graham
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201901445
Subject(s) - regioselectivity , chemistry , enol , carbanion , alkoxide , electrophile , nucleophile , trifluoromethyl , nucleophilic substitution , electrophilic substitution , deuterium , organic chemistry , catalysis , alkyl , physics , quantum mechanics
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 4 th generation refrigerant, but there have so far been few reported uses of this fluoroalkene in organic synthesis. Herein, 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 through 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.