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Copper(II) Triflate Catalyzed Amination and Aziridination of 2-Alkyl Substituted 1,3-Dicarbonyl Compounds

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journal contribution
posted on 02.05.2012 by Thi My Uyen Ton, Ciputra Tejo, Diane Ling Ying Tiong, Philip Wai Hong Chan
A method to prepare α-acyl-β-amino acid and 2,2-diacyl aziridine derivatives efficiently from Cu­(OTf)2 + 1,10-phenanthroline (1,10-phen)-catalyzed amination and aziridination of 2-alkyl substituted 1,3-dicarbonyl compounds with PhINTs is described. By taking advantage of the orthogonal modes of reactivity of the substrate through slight modification of the reaction conditions, a divergence in product selectivity was observed. In the presence of 1.2 equiv of the iminoiodane, amination of the allylic CH bond of the enolic form of the substrate, formed in situ through coordination to the Lewis acidic metal catalyst, was found to selectively occur and give the β-aminated adduct. On the other hand, increasing the amount of the nitrogen source from 1.2 to 2–3 equiv was discovered to result in preferential formal aziridination of the CC bond of the 2-alkyl substituent of the starting material and formation of the aziridine product.