Cation-n control of regiochemistry of intramolecular Schmidt reactions en route to bridged bicyclic lactams.
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.
Szostak
Michal
M
Department of Medicinal Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Malott Hall, Room 4070, Lawrence, Kansas 66045-7852, USA.
Yao
Lei
L
Aubé
Jeffrey
J
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
D019086:Bridged Bicyclo Compounds, Heterocyclic; D002412:Cations; D007769:Lactams