Total Synthesis of Lycoricidine and Narciclasine by Chemical Dearomatization of Bromobenzene

The total synthesis of lycoricidine and narciclasine is enabled by an arenophile‐mediated dearomative dihydroxylation of bromobenzene. Subsequent transpositive Suzuki coupling and cycloreversion deliver a key biaryl dihydrodiol intermediate, which is rapidly converted into lycoricidine through site‐selective syn ‐1,4‐hydroxyamination and deprotection. The total synthesis of narciclasine is accomplished by the late‐stage, amide‐directed C−H hydroxylation of a lycoricidine intermediate. Moreover, the general applicability of this strategy to access dihydroxylated biphenyls is demonstrated with several examples.