Development of Cationic Enantioselective Domino Carbopalladation/C(sp ³ )–Pd Capture Using <i>N</i> -Tosylhydrazones as Diazo Precursors

The development of cationic enantioselective domino carbopalladation/C(sp³)-Pd capture using carbenes derived from <i>N</i>-tosylhydrazones to capture the enantioenriched alkyl-Pd species is reported. This method constructs a chiral quaternary carbon center and provides direct access to chiral 3,3-disubstituted oxindoles in yields up to 91% and >99% enantioselectivity with tolerance for diverse functional groups. The involved catalytic cycle and active catalytic species have been studied via mechanistic experiments, and a rationale for the observed stereochemical outcome has been proposed by DFT analysis.