Reactivity of Vinyl Epoxides/Oxetanes/Cyclopropanes toward Arynes: Access to Functionalized Phenanthrenes.

The reactivity of vinyl epoxides/oxetanes/cyclopropanes toward arynes has been demonstrated under mild conditions to give the corresponding phenanthrenes in moderate to good yields. This transition-metal-free cascade process involves a series of Diels-Alder reaction, ring-opening aromatization, and ene reaction. Various functionalized phenanthrenes could be synthesized utilizing the versatile hydroxy group. Interestingly, vinyl epoxides/oxiranes experience preferentially the Diels-Alder reaction toward arynes over nucleophilic attack of epoxides/oxiranes.