title: Tandem beta-alkylation-alpha-arylation of amines by carbolithiation and rearrangement of N-carbamoyl enamines (vinyl ureas).
abstract: Organolithiums add in an umpolung fashion to the beta-carbon of N-carbamoyl enamines (N-vinyl ureas). The reaction proceeds with syn diastereospecificity and provides urea-stabilized, configurationally defined organolithiums. Facilitated by coordinating solvents (THF or DMPU), these undergo intramolecular attack on an N'-aryl group, resulting in retentive arylation of the organolithium and hence overall addition of an alkyl or aryl group to both carbon atoms of the urea-substituted alkene. Facile deprotection in hot butanol permits the rapid, multicomponent construction of heavily substituted amines.
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK. clayden@man.ac.uk
authors.forename: Jonathan
authors.initials: J
authors.lastname: Clayden
authors.forename: Morgan
authors.initials: M
authors.lastname: Donnard
authors.forename: Julien
authors.initials: J
authors.lastname: Lefranc
authors.forename: Alberto
authors.initials: A
authors.lastname: Minassi
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Tetlow
mesh_terms: D000478:Alkylation; D000588:Amines / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism; D014508:Urea / Q000737:chemistry*
chemical_list: D000588:Amines; D014508:Urea; D008094:Lithium