title: Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: mechanistic insight and synthetic application.
abstract: An unusual room temperature β-lactone decarboxylation facilitated a five-step enantioselective formal synthesis of the cyclopentane core of an estrogen receptor β-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 β-lactones leads to differential decarboxylation rates.
authors.affiliation: Department of Chemistry, Center for Molecular Innovation and Drug Discovery, Chemistry of Life Processes Institute, Northwestern University, Silverman Hall, Evanston, Illinois 60208, USA. scheidt@northwestern.edu.
authors.forename: Daniel T
authors.initials: DT
authors.lastname: Cohen
authors.forename: Ryne C
authors.initials: RC
authors.lastname: Johnston
authors.forename: Nicholas T
authors.initials: NT
authors.lastname: Rosson
authors.forename: Paul Ha-Yeon
authors.initials: PH
authors.lastname: Cheong
authors.forename: Karl A
authors.initials: KA
authors.lastname: Scheidt
mesh_terms: D002384:Catalysis; D003517:Cyclopentanes / Q000138:chemical synthesis / Q000737:chemistry*; D003653:Decarboxylation; D006571:Heterocyclic Compounds / Q000737:chemistry*; D007700:Kinetics; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D013237:Stereoisomerism; D013696:Temperature
chemical_list: D003517:Cyclopentanes; D006571:Heterocyclic Compounds; C030011:carbene; D008697:Methane