Applications of aziridinium ions. Selective syntheses of alpha, beta-diamino esters, alpha-sulfanyl-beta-amino esters, beta-lactams, and 1,5-benzodiazepin-2-one.
A variety of nucleophiles, including amines, thiolates, and alkoxides, were employed to open the aziridinium ions Az. The latter are opened stereospecifically and regioselectively at the C-3 position by a wide range of amines, and thiolate nucleophiles attack predominately at the C-2 position. Poor regioselectivities (ca. 1:1) were observed using nucleophiles derived from phenols, carboxylic acids, and imides. Base-mediated ring closure of the aziridinium opening products, from primary amines, gave beta-lactams and a 1, 5-benzodiazepin-2-one in high yields.
Chuang
T H
TH
Department of Chemistry and the Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Sharpless
K B
KB
D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D001388:Aziridines / Q000737:chemistry*; D001569:Benzodiazepines / Q000138:chemical synthesis* / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D004952:Esters / Q000138:chemical synthesis; D007202:Indicators and Reagents; D047090:beta-Lactams / Q000138:chemical synthesis* / Q000737:chemistry
C418322:1,5-benzodiazepin-2-one; D000588:Amines; D001388:Aziridines; D004952:Esters; D007202:Indicators and Reagents; D047090:beta-Lactams; D001569:Benzodiazepines