Arenophile-Mediated Dearomative Reduction.

A dearomative reduction of simple arenes has been developed which employs a visible-light-mediated cycloaddition of arenes with an N-N-arenophile and in situ diimide reduction. Subsequent cycloreversion or fragmentation of the arenophile moiety affords 1,3-cyclohexadienes or 1,4-diaminocyclohex-2-enes, compounds that are not synthetically accessible using existing dearomatization reactions. Importantly, this strategy also provides numerous opportunities for further derivatization as well as site-selective functionalization of polynuclear arenes.