An organocatalyzed asymmetric synthesis of fused butyrolactones via formal [2 + 2 + 2] annulation between γbutenolides, methylene indolinones, and nitroolefins in a one-pot process has been established. Products containing six contiguous stereocenters could be obtained in good yields (up to 95%) with excellent enantioselectivities (up to >99% ee) catalyzed by a L-tertleucine-derived bifunctional thiourea catalyst.

Understanding controlling factors is important for the development of the bifunctional outer-sphere C=C hydrogenations. A dominant view is that the polarization of C=C bonds is imperative for these reactions. However,...