title: Pd-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Unactivated Olefins by a Heck Reaction/Enolate Cyclization Cascade.
abstract: We disclose a Pd-catalyzed reaction protocol that regioselectively difunctionalizes unactivated olefins with aryl iodides and tethered enolates. The current method allows the rapid synthesis of a variety of 1,3,4-trisubstituted pyrrolidinones from simple and readily available amides. We further demonstrate this new method's application by postsynthetically modifying the arylacetic acid side chains of two commercial nonsteroidal anti-inflammatory drugs, indomethacin and tolmetin, to highly decorated 4-benzylpyrrolidinone frameworks. Mechanistic studies reveal that the reaction proceeds via a Heck reaction/enolate cyclization cascade, a process that exploits β-H elimination in a constructive mode for regioselective 1,2-difunctionalization of unactivated olefins.
authors.affiliation: Department of Chemistry & Chemical Biology, The University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Roshan K
authors.initials: RK
authors.lastname: Dhungana
authors.affiliation: Department of Chemistry & Chemical Biology, The University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Bijay
authors.initials: B
authors.lastname: Shrestha
authors.affiliation: Department of Chemistry & Chemical Biology, The University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Rajani
authors.initials: R
authors.lastname: Thapa-Magar
authors.affiliation: Department of Chemistry & Chemical Biology, The University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Prakash
authors.initials: P
authors.lastname: Basnet
authors.affiliation: Department of Chemistry & Chemical Biology, The University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Ramesh
authors.identifier: 0000-0002-8993-9131
authors.initials: R
authors.lastname: Giri