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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.


ABSTRACT: 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 semistabilized 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.

SUBMITTER: Li M 

PROVIDER: S-EPMC5737768 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Transition-Metal-Free Radical C(sp<sup>3</sup>)-C(sp<sup>2</sup>) and C(sp<sup>3</sup>)-C(sp<sup>3</sup>) Coupling Enabled by 2-Azaallyls as Super-Electron-Donors and Coupling-Partners.

Li Minyan M   Berritt Simon S   Matuszewski Lucas L   Deng Guogang G   Pascual-Escudero Ana A   Panetti Grace B GB   Poznik Michal M   Yang Xiaodong X   Chruma Jason J JJ   Walsh Patrick J PJ  

Journal of the American Chemical Society 20171031 45


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 semistabilized 2-azaallyl anions that behave as "super-e  ...[more]

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