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Altundas, Bilal; Alwedi, Embarek; Song, Zhihui; Gogoi, Achyut Ranjan; Dykstra, Ryan; Gutierrez, Osvaldo; Fleming, Fraser F. (, Nature Communications)Abstract A dearomatization-dislocation-coupling cascade rapidly transforms aromatic isocyanides into highly functionalized cyclohexadienes. The facile cascade installs an exceptional degree of molecular complexity: three carbon-carbon bonds, two quaternary stereocenters, and three orthogonal functionalities, a cyclohexadiene, a nitrile, and an isocyanide. The tolerance of arylisocyanides makes the method among the mildest dearomatizations ever reported, typically occurring within minutes at −78 °C. Experimental and computational analyses implicate an electron transfer-initiated mechanism involving an unprecedented isocyanide rearrangement followed by radical-radical anion coupling. The dearomatization is fast, proceeds via a complex cascade mechanism supported by experimental and computational insight, and provides complex, synthetically valuable cyclohexadienes.more » « less
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Alwedi, Embarek (, Organic Syntheses)null (Ed.)
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