High 1,3-trans Stereoselectivity in Nucleophilic Substitution at the Anomeric Position and 尾-Fragmentation of the Primary Alkoxyl Radical in 3-Amino-3-deoxy-ribofuranose Derivatives: Applicatio

详细信息    查看全文

• 作者：Alma Sa虂nchez-Eleuterio ; Leticia Quintero ; Fernando Sartillo-Piscil
• 刊名：Journal of Organic Chemistry
• 出版年：2011
• 出版时间：July 1, 2011
• 年：2011
• 卷：76
• 期：13
• 页码：5466-5471
• 全文大小：894K
• 年卷期：v.76,no.13(July 1, 2011)
• ISSN：1520-6904

文摘

The high inverse stereoselectivity in the nucleophilic substitution at the anomeric position of 3-amino-3-deoxy-ribofuranose derivatives is reported. This unprecedented stereoselectivity is explained in terms of preferential nucleophilic attack on the 鈥渋nside face鈥?of the respective five-membered ring oxocarbenium ion that orients pseudoequatorially to the benzylamine group placed at the C-3 position. In addition, an unusual 尾-fragmentation of a primary alkoxyl radical generated from its corresponding N-phthalimide derivative was achieved, and thus taking advantages of both reactions, the total synthesis of 2-epi-(鈭?-jaspine B was completed.