title: Enantiodivergent deprotonation/acylation of α-amino nitriles.
abstract: Back to 'base'ics: The title reaction of enantioenriched α-ureidonitriles was found to proceed in a highly enantiodivergent manner despite the intermediacy of stereolabile α-nitrile metallocarbanions. Enantiodivergence is dependent upon the base used. For the less basic hexamethyldisilazides (HMDS), deprotonation in which a metal (M) cation is precomplexed with an electrophile is proposed. LDA=lithium diisopropylamide.
authors.affiliation: Graduate School of Medical Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8553 (Japan) http://home.hiroshima-u.ac.jp/takedake/index-e.html.
authors.forename: Michiko
authors.initials: M
authors.lastname: Sasaki
authors.forename: Tomo
authors.initials: T
authors.lastname: Takegawa
authors.forename: Kunihiro
authors.initials: K
authors.lastname: Sakamoto
authors.forename: Yuri
authors.initials: Y
authors.lastname: Kotomori
authors.forename: Yuko
authors.initials: Y
authors.lastname: Otani
authors.forename: Tomohiko
authors.initials: T
authors.lastname: Ohwada
authors.forename: Masatoshi
authors.initials: M
authors.lastname: Kawahata
authors.forename: Kentaro
authors.initials: K
authors.lastname: Yamaguchi
authors.forename: Kei
authors.initials: K
authors.lastname: Takeda
mesh_terms: D000215:Acylation; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D003486:Cyanides / Q000737:chemistry; D008094:Lithium / Q000737:chemistry; D009570:Nitriles / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000588:Amines; D003486:Cyanides; D009570:Nitriles; D008094:Lithium
keywords: asymmetric synthesis; carbanions; cyanides; lithium; metalation