Catalytic Enantioselective Propargylation of Pyrazolones by Amide-Based Phase-Transfer Catalysts.

In this paper, we developed a highly enantioselective alkylation of 4-substituted pyrazolones catalyzed by phase-transfer catalysis. Cheap halohydrocarbons were employed as electrophilic alkylationg agents, and propargyl, allyl, and benzyl products with all-carbon quaternary stereocenters were afforded with excellent enantioselectivities and good yields. We found that the unique structures of the catalyst (hydrogen bond donors of the C-9 hydroxyl group and amide group, the triphenyl at the NH -position) were important for good enantioselectivity. Furthermore, chiral propargyl products could be easily connected to azide molecules by click cycloaddition, which offers unique opportunities to obtain structurally diverse chiral pyrazolones.