Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

详细信息    查看全文

• 作者：Andria M. Panagopoulos ; Doug Steinman ; Alexandra Goncharenko ; Kyle Geary ; Carlene Schleisman ; Elizabeth Spaargaren ; Matthias Zeller ; Daniel P. Becker
• 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：3532-3540
• 全文大小：400K
• 年卷期：v.78,no.8(April 19, 2013)
• ISSN：1520-6904

文摘

Treatment of chlorotriaryl derivatives 3a and 3d or fluorotriaryl derivatives 3b and 3e with potassium diisopropylamide afforded alkyl-shifted phenazine derivatives 5a/5b, rather than the expected 9-membered triazaorthocyclophane 2a. The phenazine derivatives were isolated in 78鈥?8% yield depending on the halogen and alkyl group present. In the absence of the halogen (chloro or fluoro), the apparent alkyl shift proceeds more slowly and cannot proceed via the intermediacy of the aryne intermediate. Mechanistic possibilities include intramolecular nucleophilic attack on an aryne intermediate leading to a zwitterionic intermediate and alkyl transfer via a 5-endo-tet process, or via a Smiles rearrangement.