Dearomatization of aromatic asmic isocyanides to complex cyclohexadienes

Bilal Altundas, Embarek Alwedi, Zhihui Song, Achyut Ranjan Gogoi, Ryan Dykstra, Osvaldo Gutierrez () and Fraser F. Fleming ()
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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

Nature Communications, 2022, vol. 13, issue 1, 1-8

Abstract: 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.

Date: 2022
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DOI: 10.1038/s41467-022-33807-7

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