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Abstract A gold(I)‐catalyzed enantioselective dearomatization is achieved via metal‐chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl‐2‐ylphosphines is developed to allow rapid access to these ligands, which in turn facilitate the application of this chemistry to a broad substrate scope including 1‐naphthols, 2‐naphthols, and phenols. Enantiomeric excesses up to 98 % are achieved via selective acceleration of one enantiomer formation enabled by hydrogen bonding between substrate and ligand remote basic group. DFT calculations lend support to the cooperative catalysis and substantiate the reaction stereochemical outcomes.
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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.more » « less
