title: Stereoelectronic Model To Explain Highly Stereoselective Reactions of Seven-Membered-Ring Oxocarbenium-Ion Intermediates.
abstract: Nucleophilic attack on seven-membered-ring oxocarbenium ions is generally highly stereoselective. The preferred mode of nucleophilic attack forms the product in a conformation that minimizes transannular interactions, thus leading to different stereoselectivity as compared to that of reactions involving six-membered-ring oxocarbenium ions.
authors.affiliation: Amgen, 360 Binney Street, Cambridge, MA, 02142, USA.
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Beaver
authors.affiliation: Department of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MNC 101-20, Pasadena, CA, 91125, USA.
authors.forename: Trixia M
authors.initials: TM
authors.lastname: Buscagan
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, NY, 10003, USA.
authors.forename: Olga
authors.initials: O
authors.lastname: Lavinda
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, NY, 10003, USA. kwoerpel@nyu.edu.
authors.forename: K A
authors.initials: KA
authors.lastname: Woerpel
mesh_terms: D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C030011:carbene; D008697:Methane
keywords: carbocations; carbohydrates; conformational analysis; electrostatic effects; stereoselectivity