A simple base-mediated tandem SN2'/SNV reaction of the readily available α-trifluoromethyl-α,β-unsaturated carbonyl compounds with N-tosylated 2-aminomalonates was developed, which provide an efficient access to functionalized tetrasubstituted 2-fluoro-2-pyrrolines in good to excellent yields. In contrast, simple 1,2-nucleophilic adducts were produced when α-trifluoromethyl styrenes were used.

A highly efficient tandem hydroamination and cyclization reaction of 2-trifluoromethyl-1,3-enynes with primary amines leading to 4-trifluoromethyl-3-pyrrolines was developed by using AgNO as a catalyst under mild reaction conditions. This new method is compatible with alkyl, aryl, and allyl primary amines, representing an atom-economical protocol for the construction of 4-trifluoromethyl-3-pyrrolines for the first time.

A simple base mediated reaction of 2-trifluoromethyl-1,3-conjugated enynes with N-acetylated 2-aminomalonates was developed, which could deliver two distinct types of products depending on substrates, i.e. 4-trifluoromethyl pyrrolidine derivatives, or gem-difluoro-1,3-conjugated enyne derivatives. Various functionalized 4-(difluoromethylene)-1,2,3,4-tetrahydropyridines could be obtained in good yields via the gold(i)-catalysed 6-endo-dig cyclization of the corresponding gem-difluoro-1,3-conjugated enynes under mild conditions.

A divergent synthesis of thioether-functionalized trifluoromethyl-alkynes, 1,3-dienes and allenes viaregioselective nucleophilic addition of sulfur nucleophiles to 2-trifluoromethyl-1,3-conjugated enynes was developed.

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