Copper(II) triflate catalyzed amination and aziridination of 2-alkyl substituted 1,3-dicarbonyl compounds
Ton, Thi My Uyen
Tiong, Diane Ling Ying
Chan, Philip Wai Hong
Date of Issue2012
School of Physical and Mathematical Sciences
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.
Journal of the American chemical society
© 2012 American Chemical Society.