Construction of a Chiral ß-Fluoroamine by Asymmetric Mannich Reaction of 2-Fluoroindanone with Pyrazolinone Ketimines.

The asymmetric Mannich reaction of 2-fluoroindanone with ketimine was developed under the catalysis of a kind of chiral copper complex, affording a chiral tetrahedral center containing fluorine. A series of ß-fluoroamine derivatives can be obtained in excellent yields (73-94%) with high diastereoselectivities (>99:1 dr) and enantioselectivities (89-99%). The possible transition state was supported by density functional theory calculation.

Construction of spirocyclic oxindole derivatives by copper-catalyzed enantioselective Michael/hemiketalization in aqueous media.

An asymmetric Michael/hemiketalization reaction between isatin-derived ß,γ-unsaturated α-ketoesters and 4-hydroxycoumarins was developed in aqueous media. A series of chiral spirooxindole derivatives with an all-carbon quaternary stereogenic center were obtained in high yields (up to 93%) and excellent enantioselectivities (up to 98%).