title: Cation-n control of regiochemistry of intramolecular Schmidt reactions en route to bridged bicyclic lactams.
abstract: The regiochemistry of the intramolecular Schmidt reaction of 2-azidoalkylketones is controlled by placing a thioether substituent at the position adjacent to the ketone to provide access to a family of unsubstituted medium bridged twisted amides. This outcome is ascribed to the presence of stabilizing through-space interactions between the diazonium cation and the n electrons on heteroatom and does not require a locked conformation of the ketone.
authors.affiliation: Department of Medicinal Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Malott Hall, Room 4070, Lawrence, Kansas 66045-7852, USA.
authors.forename: Michal
authors.initials: M
authors.lastname: Szostak
authors.forename: Lei
authors.initials: L
authors.lastname: Yao
authors.forename: Jeffrey
authors.initials: J
authors.lastname: Aubé
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D002412:Cations / Q000138:chemical synthesis / Q000737:chemistry; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D002412:Cations; D007769:Lactams