Vinylarylcyclopropanes (VACPs): All-Carbon Dipole Precursors for Controlling Linear Regioselectivity in Cycloaddition Reactions

A vinylarylcyclopropane (VACP) was synthesized via photocatalysis and employed as a 1,5-all-carbon dipole precursor in palladium-catalyzed [5 + n] cycloadditions with linear (aza)dienes or azomethine imines. This method affords eight- to nine-membered (aza)cycles in yields of up to 95%, displaying exclusive linear regioselectivity and high tolerance toward diverse functional groups. The viability of this synthetic approach was confirmed through scaled-up reactions and subsequent transformations. These findings highlight the significant utility of VACP as a versatile reagent for regioselective cycloaddition reactions.