title: Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas.
abstract: In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Michael
authors.initials: M
authors.lastname: Tait
authors.forename: Morgan
authors.initials: M
authors.lastname: Donnard
authors.forename: Alberto
authors.initials: A
authors.lastname: Minassi
authors.forename: Julien
authors.initials: J
authors.lastname: Lefranc
authors.forename: Beatrice
authors.initials: B
authors.lastname: Bechi
authors.forename: Giorgio
authors.initials: G
authors.lastname: Carbone
authors.forename: Peter
authors.initials: P
authors.lastname: O'Brien
authors.forename: Jonathan
authors.initials: J
authors.lastname: Clayden
mesh_terms: D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D008094:Lithium / Q000737:chemistry; D015394:Molecular Structure; D013034:Sparteine / Q000031:analogs & derivatives* / Q000737:chemistry*; D013237:Stereoisomerism; D014508:Urea / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000588:Amines; D014753:Vinyl Compounds; D013034:Sparteine; D014508:Urea; D008094:Lithium