2-Bromo-6-(chlorodiisopropylsilyl)phenyl tosylate as an efficient platform for intramolecular benzyne-diene [4 + 2] cycloaddition.

An intramolecular benzyne-diene [4 + 2] cycloaddition with broad substrate scope has been realized by using a cleavable silicon tether, allowing access to various polycyclic structures. 2-Bromo-6-(chlorodiisopropylsilyl)phenyl tosylate serves as an efficient platform for (1) rapid attachment of various arynophiles to the benzyne precursor via a Si-O bond and (2) facile generation of benzyne via halogen-metal exchange with Ph3MgLi.