Transition-Metal-Free Radical C(sp3)–C(sp2) and C(sp3)–C(sp3) Coupling Enabled by 2-Azaallyls as Super-Electron-Donors and Coupling-Partners

• DOI: 10.1021/jacs.7b09394
• Publication Date: 2017-10-11T20:51:39Z
• Authors: Minyan Li; Simon Berritt; Lucas Matuszewski; Guogang Deng; Ana Pascual-Escudero; Grace B. Panetti; Michal Poznik; Xiaodong Yang; Jason J. Chruma; Patrick J. Walsh
• Keywords: Reactivity; Radical ion

The past decade has witnessed the rapid development of radical generation strategies and their applications in C-C bond-forming reactions. Most these processes require initiators, transition metal catalysts, or organometallic reagents. Herein, we report discovery a simple organic system (2-azaallyl anions) that enables coupling reactions under transition-metal-free conditions. Deprotonation N-benzyl ketimines generates semistabilized 2-azaallyl anions behave as "super-electron-donors" (SEDs) reduce aryl iodides alkyl halides to radicals. SET process converts into persistent radicals, which capture radicals form bonds. with makes possible synthesis functionalized amine derivatives without use exogenous initiators catalysts. Radical clock studies anion provide mechanistic insight for this unique reactivity.