Development of Transition-Metal-Catalyzed Dearomatization Reactions.

ABSTRACT

To develop dearomatization reactions based on a nucleophilic activation of phenols, naphthols, and indoles, ipso-Friedel-Crafts-type C-alkylation must be selectively promoted over competitive O- or N-alkylation reactions. Resolving this chemoselectivity issue is essential for developing this class dearomatization reaction. We found that various dearomatization reactions could be developed using appropriately designed aromatic substrates with an electrophilic moiety for intramolecular reactions. This review describes the transition-metal-catalyzed dearomatization reactions developed by our group. π-Allylpalladium species, η3-propargylpalladium species, alkynes activated by Au(I) species, and silver carbene species could be applied as electrophiles in our reaction system, which provided access to a wide variety of dearomatized products from planar aromatic compounds in a highly chemoselective manner.