Enantioselective Desymmetrizing Hydroalkoxylation of 1,4-and 1,8-Diynes Enabled by Chiral Bronsted Acid Catalysis

Herein,an organocatalytic enantioselective desymmetrizing hydroalkoxylationof 1,4- and 1,8-diynes is disclosed, which represents a unique chiralBronsted acid-catalyzed desymmetrization of diynes. This protocolprovides a facile and practical access to enantioenriched 1,3-diaminopropanolderivatives and & gamma;-butyrolactones with a wide substrate scopeand generally high enantioselectivities. Besides, the backbones ofthese products constitute the structural core of numerous bioactivemolecules, and they can serve as valuable precursors for the expeditiousassembly of versatile N- and O-heterocycles. Moreover, control experimentsand theoretical calculations are employed to confirm the mechanisticrationale and elucidate the origin of enantioinduction.