Catalytic Dearomative [1,5]‐Sigmatropic Carbon Shift of Heterole‐Fused Norcaradienes Enabled Concise Helicenation

In contrast to the locked fluxionality of norcaradienes fused by benzene, unexplored less aromatic heterole-fused norcaradienes, creatively generated by intramolecular hydroarylation of heteroaryl alkynylcyclopropanes, reserve a balancing fluxionality that permits a dearomative [1,5]-sigmatropic carbon shift of norcaradienes akin to the reduced aromaticity of heterole. This "walk" shift was confirmed by the isolation of a cycloheptatriene species derived from ring-expansion of a dearomatized alkynylated heterole-fused norcaradiene. A following ester-directed ring-opening rearomatization of these dearomatized heterole-fused norcaradienes gives the products featuring migratory acylmethyls that are competent for helicenation with the neighboring (hetero) arenes via (formal) dehydrative alkenylation. Such balancing reactivity of heterole-fused norcaradienes will open up the opportunity for the development of controllable reactions of fused norcaradienes.