Dearomatization of aromatic asmic isocyanides to complex cyclohexadienes. Academic Article uri icon


  • 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 -78C. 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.

published proceedings

  • Nat Commun

author list (cited authors)

  • Altundas, B., Alwedi, E., Song, Z., Gogoi, A. R., Dykstra, R., Gutierrez, O., & Fleming, F. F.

complete list of authors

  • Altundas, Bilal||Alwedi, Embarek||Song, Zhihui||Gogoi, Achyut Ranjan||Dykstra, Ryan||Gutierrez, Osvaldo||Fleming, Fraser F

publication date

  • January 2022