title: Rhodium-catalyzed sequential allylic amination and olefin hydroacylation reactions: enantioselective synthesis of seven-membered nitrogen heterocycles.
abstract: Dynamic kinetic asymmetric amination of branched allylic acetimidates has been applied to the synthesis of 2-alkyl-dihydrobenzoazepin-5-ones. These seven-membered-ring aza ketones are prepared in good yield with high enantiomeric excess by rhodium-catalyzed allylic substitution with 2-amino aryl aldehydes followed by intramolecular olefin hydroacylation of the resulting alkenals. This two-step procedure is amenable to varied functionality and proves useful for the enantioselective preparation of these ring systems.
authors.affiliation: Department of Chemistry, The University of Iowa, Iowa City, IA 52242 (USA) http://chem.uiowa.edu/nguyen-research-group.
authors.forename: Jeffrey S
authors.initials: JS
authors.lastname: Arnold
authors.forename: Edward T
authors.initials: ET
authors.lastname: Mwenda
authors.forename: Hien M
authors.initials: HM
authors.lastname: Nguyen
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000475:Alkenes; D012238:Rhodium
keywords: allylic amination; asymmetric catalysis; intramolecular hydroacylation; nitrogen heterocycles; rhodium