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Benzyne-[2 + 2] cycloadditions with enamides are described. This effort led to the development of a highly stereoselective tandem [2 + 2] cycloaddition-pericyclic ring-opening-intramolecular-N-tethered-[4 + 2] cycloaddition for rapid assembly of nitrogen heterocycles.

Enamide-Benzyne-[2 + 2] Cycloaddition: Stereoselective Tandem [2 + 2]−Pericyclic Ring-Opening−IntramolecularN-Tethered [4 + 2] Cycloadditions