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

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• 作者：Thi My Uyen Ton ; Ciputra Tejo ; Diane Ling Ying Tiong ; Philip Wai Hong Chan
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：May 2, 2012
• 年：2012
• 卷：134
• 期：17
• 页码：7344-7350
• 全文大小：459K
• 年卷期：v.134,no.17(May 2, 2012)
• ISSN：1520-5126

文摘

A method to prepare 伪-acyl-尾-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鈺怤Ts 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鈥擧 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 尾-aminated adduct. On the other hand, increasing the amount of the nitrogen source from 1.2 to 2鈥? equiv was discovered to result in preferential formal aziridination of the C鈥擟 bond of the 2-alkyl substituent of the starting material and formation of the aziridine product.