Stereoselective 1,2-Dicarbofunctionalization of Trisubstituted Alkenes by Palladium-Catalyzed Heck/Suzuki or Heck/Sonogashira Domino Sequence

Highly enantioselective and diastereoselective 1,2-diarylation and 1,2-arylalkynylation of trisubstituted alkenes are reported via the palladium-catalyzed Heck/Suzuki or Heck/Sonogashira domino sequence. These alkenes represent an extension of enantioselective dicarbofunctionalization from terminal alkenes to trisubstituted ones based on anionic capture of the secondary alkyl-Pd intermediate. A wide range of 3,3'-spirooxindoles, featuring vicinal spiro quaternary and tertiary stereocenters, is efficiently constructed in one step with up to 94% enantioselectivities and excellent diastereoselectivities (>19:1 dr). The practicability of this method is shown by its broad substrate scope and versatile transformations of the resulting products. [GRAPHICS] .