Palladium-Catalyzed Dearomative para-/ortho-Cycloaddition Cascades of N-Allylanilines with 1,4-Enynes and CO via Skeletal Reorganization

A selectivity-control approach for palladium-catalyzed dearomative para-/ortho-cycloaddition cascades of aromatic compounds with 1,4-enynes and CO via a skeletal reorganization process to produce polycycle-fused bicyclo[2.2.2]octenes is reported. This mechanistically novel process depends on a skeletal reorganization that consists of a sequence of dearomative [4 + 2] para-cycloaddition, 3,3-Cope rearrangement, and carbon-carbon bond activation/[4 + 2] cycloaddition.