| Autor: |
Minyan, Li, Simon, Berritt, Lucas, Matuszewski, Guogang, Deng, Ana, Pascual-Escudero, Grace B, Panetti, Michal, Poznik, Xiaodong, Yang, Jason J, Chruma, Patrick J, Walsh |
| Rok vydání: |
2017 |
| Předmět: |
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| Zdroj: |
Journal of the American Chemical Society. 139(45) |
| ISSN: |
1520-5126 |
| Popis: |
The past decade has witnessed the rapid development of radical generation strategies and their applications in C–C bond-forming reactions. Most of these processes require initiators, transition metal catalysts or organometallic reagents. Herein, we report the discovery of a simple organic system (2-azaallyl anions) that enables radical coupling reactions under transition-metal-free conditions. Deprotonation of N-benzyl ketimines generates semi-stabilized 2-azaallyl anions that behave as “super-electron-donors” (SEDs) and reduce aryl iodides and alkyl halides to aryl and alkyl radicals. The SET process converts the 2-azaallyl anions into persistent 2-azaallyl radicals, which capture the aryl and alkyl radicals to form C–C bonds. The radical coupling of aryl and alkyl radicals with 2-azaallyl radicals makes possible the synthesis of functionalized amine derivatives without the use of exogenous radical initiators or transition metal catalysts. Radical clock studies and 2-azaallyl anion coupling studies provide mechanistic insight for this unique reactivity. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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