Reactions of CF3-Haloenones with 1,3-Dicarbonyl Compounds: Chemo- and Stereoselective Assembly of Fluorinated Dihydrofurans

•A simple one-pot, atom and steps economic (PASE) synthesis of trifluoromethylated dihydrofurans has been elaborated.•The assembly of heterocycles from fluorinated α-haloenones and 1,3-dicarbonyls is initiated by aza-Michael reaction.•The different reaction pathways of CF3-haloenones and 1,3-N,N- or 1,3-C,O-binucleophiles was found. The chemo- and stereoselective one-pot synthesis of functionalized trifluoromethylated 4,5-dihydrofurans was developed. It consists in the treatment of fluorinated 2-haloenones with 1,3-dicarbonyl compounds (1,3-diketones and β-keto esters). The reaction was generally found to proceed in moderate to good yield and excellent selectivity. The mechanism of the assembly of these heterocycles is discussed in terms of multi-step processes involving formation of Michael adduct followed by cyclization through the classical intramolecular halogen nucleophilic substitution at sp3 carbon atom. [Display omitted]