Self-Catalyzed Mannich-Type Reaction of Enolizable Cyclic 1,3-Dicarbonyls to Acyclic Nitrones: An Entry to Functionalized 尾-Enamino Diones

详细信息    查看全文

• 作者：Massimiliano Cordaro ; Francesco Risitano ; Angela Scala ; Antonio Rescifina ; Ugo Chiacchio ; Giovanni Grassi
• 刊名：The Journal of Organic Chemistry
• 出版年：2013
• 出版时间：April 19, 2013
• 年：2013
• 卷：78
• 期：8
• 页码：3972-3979
• 全文大小：381K
• 年卷期：v.78,no.8(April 19, 2013)
• ISSN：1520-6904

文摘

A new method for the preparation of highly functionalized 尾-enamino diones has been developed. The protocol involves an initial self-catalyzed Mannich-type reaction of enolizable cyclic 1,3-dicarbonyls to nitrones, followed by a spontaneous intramolecular reorganization of the resulting nonisolated hydroxylamine to enamino derivatives. These compounds retain the features of unnatural 伪-amino acids. The ease of preparation makes them attractive intermediates for the synthesis of peptidomimetics, polyheterocycles, and other multifunctional compounds. All experimental results have been efficiently rationalized by in silico studies at the M06-2X level of theory, and a valid mechanistic pathway has been proposed.