Catalytic Asymmetric Piancatelli Rearrangement: BrOnsted Acid Catalyzed 4Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral BrOnsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.