Radical Cyclizations of Cyclic Ene Sulfonamides Occur with 尾-Elimination of Sulfonyl Radicals to Form Polycyclic Imines

详细信息    查看全文

• 作者：Hanmo Zhang ; E. Ben Hay ; Steven J. Geib ; Dennis P. Curran
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：November 6, 2013
• 年：2013
• 卷：135
• 期：44
• 页码：16610-16617
• 全文大小：486K
• 年卷期：v.135,no.44(November 6, 2013)
• ISSN：1520-5126

文摘

Radical cyclizations of cyclic ene sulfonamides provide stable bicyclic and tricyclic aldimines and ketimines in good yields. Depending on the structure of the precursor, the cyclizations occur to provide fused and spirocyclic imines with five-, six-, and seven-membered rings. The initial radical cyclization produces an 伪-sulfonamidoyl radical that undergoes elimination to form the imine and a phenylsulfonyl radical. In a related method, 3,4-dihydroquinolines can also be produced by radical translocation reactions of N-(2-iodophenylsulfonyl)tetrahydroiso-quinolines. In either case, very stable sulfonamides are cleaved to form imines (rather than amines) under mild reductive conditions.