Bifunctional Phosphine Ligand Enabled Gold-Catalyzed Alkynamide Cycloisomerization: Access to Electron-Rich 2-Aminofurans and Their Diels-Alder Adducts

Angew Chem Int Ed Engl. 2019 Nov 25;58(48):17180-17184. doi: 10.1002/anie.201908598. Epub 2019 Oct 15.

Abstract

By using biphenyl-2-ylphosphines functionalized with a remote tertiary amino group as a ligand, readily available acetylenic amides are directly converted into 2-aminofurans devoid of any electron-withdrawing and hence deactivating/stabilizing substituents. These highly electron-rich furans have rarely been prepared, let alone applied in synthesis, because of their high reactivities and low stabilities associated with the electron-rich nature of the furan ring. In this work, these reactive furans smoothly undergo either in situ intermolecular Diels-Alder reactions to deliver highly functionalized/substituted aniline products or intramolecular ones to furnish carbazole-4-carboxylates in mostly good to excellent yields. This work offers general and expedient access to this class of little studies electron-rich furans and should lead to exciting opportunities for their applications.

Keywords: Diels-Alder reactions; dienes; gold; heterocycles; isomerizations.