Thioether-functionalized trifluoromethyl-alkynes, 1,3-dienes and allenes: divergent synthesis from reaction of 2-trifluoromethyl-1,3-conjugated enynes with sulfur nucleophiles.

A divergent synthesis of thioether-functionalized trifluoromethyl-alkynes, 1,3-dienes and allenes regioselective nucleophilic addition of sulfur nucleophiles to 2-trifluoromethyl-1,3-conjugated enynes was developed. The addition patterns depend on the type of enyne, sulfur nucleophile and reaction conditions used. 1,4-Addition leading to thioether-functionalized trifluoromethyl-allenes was realized when enynes possessing electron-withdrawing aryl groups on the alkyne moiety were used as reaction partners and alkanethiols were used as nucleophiles, whereas solvent-controlled construction of thioether-functionalized 1,3-dienes and alkynes was realized, respectively, a 3,4-addition pattern or 1,2-addition pattern if thiophenols were applied as nucleophiles.