Dearomatization reactions represent an important class of transformations in the organic chemist's toolbox, having received significant attention and synthetic application in recent years. However, dearomative transformations for simple arenes that also introduce functionality are much less developed. We have recently disclosed a functionalization platform that employs small molecules, termed arenophiles, to facilitate dearomative dihydroxylation and diaminodihydroxylation of simple arenes. Utilizing photoinduced arenophile <i>para</i>-cycloaddition, followed by osmium-catalyzed dihydroxylation, we can access single constitutional isomers of the product of formal dihydroxylation of a single alkene in the arene substrate. In the presented research, we have developed a unique Narasaka-Sharpless dihydroxylation/Suzuki coupling sequence that enables rapid access to dihydroxylated biphenyls. Dearomative dihydroxylation of bromobenzene, followed by transpositional Suzuki coupling, permits the incorporation of a variety of substituted arylboronic acids into the carbon framework of the dearomatized product. Moreover, we have applied this strategy to the expedient synthesis of the anti-cancer alkaloid lycoricidine, starting from feedstock bromobenzene and a simple arylboronic acid.

Total synthesis of lycoricidine through chemical dearomatization of bromobenzene

253rd National Meeting (2017)

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