Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: mechanistic insight and synthetic application

摘要

An unusual room temperature beta-lactone decarboxylation facilitated a five-step enantioselective formal synthesis of the cyclopentane core of an estrogen receptor beta-agonist. A computational study probed the underlying factors facilitating unprecedented, rapid decarboxylation. Aryl substitution promotes faster reaction in the retro-2+2 as a result of conjugative stabilization with the forming olefin. Additionally, the configuration of the alpha-ester in these fused beta-lactones leads to differential decarboxylation rates.