Diastereoselective Stereo-Divergent Synthesis of Spiroindolines via Ligand-Controlled Silver(I)-Catalyzed Asymmetric [3 + 2] cycloadditions.

A series of spirocyclic pyrrolidine derivatives with quaternary stereocenters was constructed via asymmetric [3 + 2] cycloaddition reactions between imino esters and 2-oxindole. By ingenious use of ligands on the silver catalyst allows stereoselectivity to either endo -isomers (ee up to 98 %, yields up to 96 %) with (R , Rp)-Ph-Phosferrox or exo -isomers (ee up to 99 %, yields up to 87 %) with (R)-BINAP. This work is notable for its high yields, broad substrate adaptability and excellent enantioselectivity. [Display omitted] • This methodology offers an efficient pathway for the concurrent synthesis of spirocyclic pyrrolidine derivatives containing a tetradentate stereocenter through exocyclic addition and endocyclic addition. • By ingenious use of ligands on the silver catalyst allows stereoselectivity to either endo-isomers (ee up to 98 %, yields up to 96 %) with (R, Rp)- Ph-Phosferrox or exo-isomers (ee up to 99 %, yields up to 87 %) with (R)-BINAP. • Efficient catalytic synthesis of chiral molecules has been realized. [ABSTRACT FROM AUTHOR]