Dearomative Intramolecular meta-Thermocycloadditions of Benzene Rings via Wheland Intermediates.

Dearomative cycloadditions are powerful synthetic transformations utilizing aromatic compounds for cycloaddition reactions. They have been extensively applied to the synthesis of biologically relevant compounds not only because of the complexity generated from simplicity but also the atom- and step-economy. For the most studied yet challenging benzene ring systems, ortho- and para-cycloadditions have been realized both photochemically and thermally, while the meta-cycloadditions are still limited to the photochemical processes tracing back to the 1960s. Herein, we for the first time realized the thermal cycloadditions of benzene rings with alkenes in a meta fashion via Wheland intermediates. A broad spectrum of readily available C(sp2)-rich aniline-tethered enynes were transformed into C(sp3)-rich 3D complex polycyclic architectures simply by stirring in TFA. Moreover, the reaction could be performed in gram-scales and the products could be diversely elaborated.