Stereoselective synthesis of chiral 2,3-cis-2-ethynylaziridines by base-mediated intramolecular amination of bromoallenes.
[reaction: see text] Novel stereoselective synthesis of 2,3-cis-2-ethynylaziridines from amino allenes is presented. While sodium hydride mediated intramolecular amination of (4S,aS)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes yields a mixture of 2,3-cis- and 2,3-trans-2-ethynylaziridines in which the cis-isomer predominates (79:21-89:11), the amination of (4S,aR)-isomers affords 2,3-cis-aziridines in excellent selectivities (91:9-100:0). Conversion of 2,3-trans-2-ethynylaziridines into the corresponding cis-isomers via a sequence of reactions (methanesulfonic acid mediated ring-opening reaction, bromination, and aziridination) is also described.
Ohno
H
H
Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan.
Hamaguchi
H
H
Tanaka
T
T
D000466:Alkadienes / Q000737:chemistry*; D000586:Amination; D001388:Aziridines / Q000138:chemical synthesis*; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D013237:Stereoisomerism
D000466:Alkadienes; D001388:Aziridines; D006842:Hydrocarbons, Brominated; C025947:propadiene