Simple and efficient copper(II) pyridine complexes for fast olefin aziridination at 1 : 1 olefin : PhINTs ratio

CHED 226

Seth A Binfield, sbinfiel@wam.umd.edu1, Fabian Mohr1, James C. Fettinger1, and Andrei N. Vedernikov, avederni@umd.edu2. (1) Department of Chemistry and Biochemistry, University of Maryland at College Park, Bdg. 091, College Park, MD 20742, (2) Department of Chemistry and Biochemistry, University of Maryland, Bdg. 091, College Park, MD 20742
Aziridines are important synthetic intermediates in modern organic syntheses. One of the methods to prepare aziridines is by reacting olefins with suitable sources of nitrenes such as iminoiodinanes. The most important limitations of this method are high catalyst loadings (up to 5%) and high olefin to iminoiodinane ratio. We found that four-coordinate dichlorocopper(II) pyridine-based complexes exhibit high catalytic activity in aziridination of regular olefins with PhINTs in the presence of 1-2 equivalents of NaBArF4 (BArF4 = tetrakis[3,5-di(trifluoromethyl)phenyl]borate). Reactive olefins, styrene, tri- and tetramethylethylene, gave yields exceeding 90% with a 1:1 olefin : PhINTs ratio and 1-5 mol% catalyst loading. cis-Cyclooctene, indene, methyl acrylate, methyl methacrylate, vinyl methyl ketone, tert-butylethylene, neo-pentylethylene, 1-hexene, and cyclopentene showed yields varying from 44 to 83%. The catalytic activity and efficiency of the copper complexes decrease moderately in the absence of NaBArF4.
 

Undergraduate Research Poster Session: Organic Chemistry
2:00 PM-4:00 PM, Monday, 29 August 2005 Washington DC Convention Center -- Hall A, Poster

Division of Chemical Education

The 230th ACS National Meeting, in Washington, DC, Aug 28-Sept 1, 2005