Electronic properties of the ligands switch the diastereoselectivity in the Cu‐catalyzed 1,3‐dipolar cycloaddition of azomethine ylides to nitroalkenes: exo‐ or endo‐pyrrolidines were obtained with high diastereo‐ and enantioselectivities in the presence of different chiral (phosphanylferrocenyl)oxazoline ligands (e.g. 3 a, b).

A novel P(NMe2)3-mediated reductive [1+4] annulation reaction between isatins and enones has been developed, providing the facile synthesis of spirooxindole-dihydrofurans. This reaction unveils the first practical approach to construct five-membered cyclic motifs via a Kukhtin-Ramirez adduct involved [1+4] annulation mode.

The first interrupted asymmetric hydroaminomethylation reaction was developed. The challenging trans-1,2-disubstituted olefins were employed as substrates, and a series of valuable chiral pyrrolidinones and pyrrolidines were obtained in high yields with high regioselectivities and excellent enantioselectivities. Several synthetic transformations were conducted, demonstrating the high synthetic utility of our method. A creative route for the synthesis of vernakalant and Enablex was also developed.