Abstract: | A novel palladium‐catalyzed three‐component reaction of phenol‐derived biaryls with N‐benzoyloxyamines and norbornadiene (NBD) has been developed for the assembly of highly functionalized spiroindenes. This domino process was realized through NBD‐assisted C−H amination and phenol dearomatization by forming one C−N bond and two C−C bonds in a single step. Preliminary studies indicated that asymmetric control of this transformation was feasible with chiral ligands. Moreover, the potential synthetic utility of this methodology was highlighted by a series of further transformations. |