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

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.