We recently explored the possibility of using gold(I) catalysts to activate allenes towards alcohol nucleophiles to effect allenoate Claisen rearrangements. However, instead of allene activation, a pendant ester was transesterified and etherified, which led to our development of a gold-catalyzed, microwave protocol to activate alcohols to form ethers and amines via an intermolecular, SN1-type reaction. Ultimately, in lieu of a metal-catalyzed version, we have developed a Bronsted acid-catalyzed allenoate Claisen that affords the corresponding products in high yields and enantioselectivities. Lessons learned from these studies have led to the serendipitous discovery of a silver-catalyzed, N-formylation reaction and have informed our development of an anti-Markovnikov hydroamination reaction.








Scott Denmark(University of Illinois) , Noah Burns(Stanford University) , Anna Wenzel(Claremont McKenna College)