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

ABSTRACT

An unusual room temperature ß-lactone decarboxylation facilitated a five-step enantioselective formal synthesis of the cyclopentane core of an estrogen receptor ß-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 α-ester in these fused ß-lactones leads to differential decarboxylation rates.