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Dearomatization of aromatic asmic isocyanides to complex cyclohexadienes

Author

Listed:
  • Bilal Altundas

    (Drexel University)

  • Embarek Alwedi

    (Merck Inc.)

  • Zhihui Song

    (University of Maryland)

  • Achyut Ranjan Gogoi

    (Texas A&M University)

  • Ryan Dykstra

    (University of Maryland)

  • Osvaldo Gutierrez

    (Texas A&M University)

  • Fraser F. Fleming

    (Drexel University)

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.

Suggested Citation

  • Bilal Altundas & Embarek Alwedi & Zhihui Song & Achyut Ranjan Gogoi & Ryan Dykstra & Osvaldo Gutierrez & Fraser F. Fleming, 2022. "Dearomatization of aromatic asmic isocyanides to complex cyclohexadienes," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33807-7
    DOI: 10.1038/s41467-022-33807-7
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