Metal-Catalyzed Spiroannulation-Fluoromethylfunctionaliztions of 1,5-Enynes for the Synthesis of Stereodefined (Z)-Spiroindenes.

Two classes of new catalytic spiroannulation-fluormethylfunctionaliztions of para-quinone methide (p-QM)-containing 1,5-enynes have been established under redox-neutral conditions. Palladium-catalyzed spiroannulation-iododifluoromethylation with ethyl difluoroiodoacetate oriented completely stereoselective access to (Z)-spiroindenes and the latter included copper-catalyzed three-component spiroannulation-cyanotrifluoromethylation starting from Togni's reagent and trimethylsilanecarbonitrile (TMSCN). Both reaction pathways involve fluoroalkyl radical-triggered 1,6-addition/5-exo-dig annulation/metal radical cross-coupling/reductive elimination sequence, providing practical and stereoselective protocols for rapidly constructing cyclohexadienone-containing spiroindenes with generally good yields.