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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

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

Language: Английский

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

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

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

Language: Английский