Efficient aziridination of olefins catalyzed by mixed-valent dirhodium(II,III) caprolactamate.
[reaction: see text] A mild, efficient, and selective aziridination of olefins catalyzed by dirhodium(II) caprolactamate [Rh(2)(cap)(4).2CH(3)CN] is described. Use of p-toluenesulfonamide (TsNH(2)), N-bromosuccinimide (NBS), and potassium carbonate readily affords aziridines in isolated yields of up to 95% under extremely mild conditions with as little as 0.01 mol % Rh(2)(cap)(4). Aziridine formation occurs through Rh(2)(5+)-catalyzed aminobromination and subsequent base-induced ring closure. An X-ray crystal structure of a Rh(2)(5+) halide complex, formed from the reaction between Rh(2)(cap)(4) and N-chlorosuccinimide, has been obtained.
Catino
Arthur J
AJ
Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
Nichols
Jason M
JM
Forslund
Raymond E
RE
Doyle
Michael P
MP
D000475:Alkenes / Q000737:chemistry*; D001388:Aziridines / Q000138:chemical synthesis*; D002384:Catalysis; D007202:Indicators and Reagents; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
D000475:Alkenes; D001388:Aziridines; D007202:Indicators and Reagents; D009942:Organometallic Compounds; D012238:Rhodium