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

• Published in: Journal of the American Chemical Society Vol. 134; no. 17; pp. 7344 - 7350
• Main Authors: Ton, Thi My Uyen, Tejo, Ciputra, Tiong, Diane Ling Ying, Chan, Philip Wai Hong
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 02-05-2012
• Subjects: Amination; Amino Acids - chemical synthesis; Amino Acids - chemistry; Aziridines - chemical synthesis; Aziridines - chemistry; Catalysis; Copper - chemistry; Phenanthrolines - chemical synthesis; Phenanthrolines - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja301415k

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.