A strategy for the facile construction of the chiral quinolinylmethanolic structure, a core featured in cinchona alkaloids, is reported. A new reactivity is harnessed by TfOH-promoted chemoselective activation of α-C-H over O-H bond in quinolinylmethanols. The new reactivity is successfully engineered with an iminium catalysis in a synergistic manner to create a powerful conjugate addition-cyclization cascade process for synthesis of chiral quinoline derived γ-butyrolactones in good yields and with good to excellent enantioselectivities. The method enables the first total synthesis of natural product broussonetine in three steps.

Metal free 1,3-dipolar cycloaddition between alkenylazaarenes and nitrones has been developed for the synthesis of 4-substituted isoxazolidines and 5-substituted isoxazolidines in good yields and selectivities.

A chiral amine catalyzed enantioselective α-functionalization of α-substituted β-ketocarbonyls with electron-deficient vinylarenes has been developed to construct the dicarbonyl products with the formation of a chiral all-carbon quaternary stereocenter. The products can be used for the efficient synthesis of useful but challenging chiral quaternary centered pyrazolones.

Construction of an All-Carbon Quaternary Stereocenter by Organocatalytic Enantioselective -Functionalization of -Substituted -Ketocarbonyls with Electron Deficient Vinylarenes. -The enantioselective reaction of ketones (II) and (VI) with vinylarenes (I) gives rise to desired dicarbonyl compounds (III) and (VII), which are readily converted into chiral pyrazolones (V) and (VIII), respectively. -(LIU, S.; TONG, M.; YU, Y.; XIE, H.; LI, H.; WANG*, W.; Chem. Commun. (Cambridge) 51 (2015) 56, 11221-11224, http://dx.