Core Structure‐Based Design of Organocatalytic [3+2]‐Cycloaddition Reactions: Highly Efficient and Stereocontrolled Syntheses of 3,3′‐Pyrrolidonyl Spirooxindoles

Extraordinary levels of stereocontrol were achieved in an efficient organocatalytic asymmetric [3+2]-cycloaddition reaction between an α-isothiocyanato imide and various methyleneindolinones. Simple precursors were used for the rapid construction of spirocyclic oxindole derivatives with high enantiopurity and structural diversity, thus providing a new avenue of significance to medicinal chemistry and diversity-oriented synthesis.