Herein, we report
a multistep one-pot reaction of substituted pyridines
leading toN-protected tetrahydropyridines with outstanding
enantioselectivity (up to 97% ee). An iridium(I)-catalyzed dearomative
1,2-hydrosilylation of pyridines enables the use ofN-silyl enamines as a new type of nucleophile in a subsequent palladium-catalyzed
asymmetric allylic alkylation. This telescoped process overcomes the
intrinsic nucleophilic selectivity of pyridines to synthesize enantioenriched,
C-3-substituted tetrahydropyridine products that have been otherwise
challenging to access.