Thiophene-Fused Bisdehydro[12]annulene That Undergoes Transannular Alkyne Cycloaddition by Either Light or Heat

Aiko Fukazawa *†, Hiroya Oshima †, Yoshihito Shiota #, Shouya Takahashi #, Kazunari Yoshizawa *#, and Shigehiro Yamaguchi *†‡§

A new bisdehydro[12]annulene derivative having a thiophene-fused structure has been synthesized. This highly twisted π-conjugated macrocycle with two acetylene moieties in close proximity produces a [2+2]-type alkyne cycloadduct by either photoirradiation or mild heating without any transition metals. Theoretical calculations reveal that the thermal reaction proceeds through successive 8π and 4π electrocyclic reactions, while the photochemical reaction is an asynchronous concerted [2+2] cycloaddition. The fused structure with the less-aromatic thiophene ring is crucial for achieving this reaction. The cycloadduct, thiophene-fused biphenylene, has significant potential as a new polycyclic π-scaffold for electronic applications.