A palladium-catalyzed dearomative diarylation of C2-deuterated
or C2-nonsubstituted indoles through domino Heck/Suzuki coupling is
established. Relying on electron-deficient phosphite ligand, side
reactions including intermolecular Suzuki coupling and intramolecular
C–D/H arylation are inhibited and a wide range of 2,3-diarylated
indolines bearing vicinal tertiary stereocenters including deuterated
ones are afforded in moderate to excellent yields (up to 94%) and
excellent diastereoselectivities (>20:1). The catalyst loading
can
be lowered to 0.02 mol % at elevated temperature.