Bifunctional Borane Catalysis of a Hydride Transfer/Enantioselective [2+2] Cycloaddition Cascade

Herein, we present a mild and efficient method for synthesizing enantioenriched tetrahydroquinoline-fused cyclobutenes through a cascade reaction between 1,2-dihydroquinolines and alkynones with catalysis by chiral spiro-bicyclic bisboranes. The bisboranes served two functions: first they catalyzed a hydride transfer to convert the 1,2-dihydro-quinoline substrate to a 1,4-dihydroquinoline, and then they activated the alkynone substrate for an enantioselective [2+2] cycloaddition reaction with the 1,4-dihydroquinoline generated in situ.