Cu-Catalyzed Direct Enantioselective Vinylogous Mannich Reaction between ß,γ-Unsaturated Pyrazoleamides and Ketimines.

A catalytic asymmetric vinylogous Mannich-type reaction between ß,γ-unsaturated amides and ketimines has been developed in excellent regio-, diastereo-, and enantioselectivities. The methodology provides an efficient approach to construct chiral homoallylic amines with a 3-amino-2-oxindole scaffold. Moreover, the transformations of the chiral products, including the removal of the pyrazole group or Boc group, the reduction of the C-C double bond, and Suzuki coupling, have been investigated.

Copper-catalyzed enantioselective alkynylation of pyrazole-4,5-diones with terminal alkynes.

A copper-catalyzed enantioselective alkynylation between terminal alkynes and pyrazole-4,5-diones has been developed. With 2.5 mol% CuI and 3 mol% chiral ligand L15, chiral propargylic alcohols bearing a pyrazolone motif were produced in 82-99% yield and up to 98% ee. Moreover, both enantiomers of the chiral propargylic alcohols were obtained with ligands L12 and L15, respectively.