Gold‐Catalyzed One‐Pot Cycloisomerization/Nucleophilic Addition/Rearrangement of Acenaphthylene Carbaldehyde Derivatives
Alexis Truchon, Aurélien Dupeux, Sandra Olivero, Véronique Michelet
Abstract
Abstract Merging the latest advances in the field of gold catalysis and the efficiency of hexafluoro‐2‐propanol (HFIP), a gold‐catalyzed orthogonal tandem reaction has been developed to access carbocyclic ketone on naphthalene substrates. The methodology involved a cycloisomerization/nucleophilic addition and a C→O rearrangement. The HFIP solvent most probably acted as a Lewis‐acid on isochromene derivatives, through hydrogen donor bond activity. A large range of acenaphthylene carbaldehyde has been engaged in this process coupling gold catalysis and Lewis‐acid behavior of HFIP leading to cyclic ketones with a yield ranging from 15 to 91% (27 compounds). The mechanism was investigated, and the reaction most presumably occurred via a classical cyclization process followed by a [Au]‐HFIP interaction for the final rearrangement. The interest of such transformation was demonstrated by performing it on a gram‐scale. Moreover, a post‐functionalization bromination was performed, as well as the isomerization of some functionalized ketones leading to full trans derivatives with a yield ranging from 78 to 90% yields.