69939-39-5Relevant academic research and scientific papers
2-Azaallyl Anions as Light-Tunable Super-Electron-Donors: Coupling with Aryl Fluorides, Chlorides, and Bromides
Wang, Qianmei,Poznik, Michal,Li, Minyan,Walsh, Patrick J.,Chruma, Jason J.
, p. 2854 - 2868 (2018/08/17)
Herein, we present 2-azaallyl anions as colored super-electron-donors capable of reducing a collection of aryl halides via a single electron transfer and coupling with the corresponding radicals to forge new C?C bonds. This offers a robust approach for th
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
Li, Minyan,Berritt, Simon,Matuszewski, Lucas,Deng, Guogang,Pascual-Escudero, Ana,Panetti, Grace B.,Poznik, Michal,Yang, Xiaodong,Chruma, Jason J.,Walsh, Patrick J.
supporting information, p. 16327 - 16333 (2017/11/22)
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.
Synthesis of (diarylmethyl)amines using Ni-catalyzed arylation of C(sp3)-H bonds
Fernández-Salas, José A.,Marelli, Enrico,Nolan, Steven P.
, p. 4973 - 4977 (2015/07/27)
The first nickel catalyzed deprotonative cross coupling between C(sp3)-H bonds and aryl chlorides is reported, allowing the challenging arylation of benzylimines in the absence of directing group or stoichiometric metal activation. This methodo
Palladium-catalyzed regioselective arylation of 1,1,3-triaryl-2-azaallyl anions with aryl chlorides
Li, Minyan,Berritt, Simon,Walsh, Patrick J.
supporting information, p. 4312 - 4315 (2014/10/15)
A regioselective arylation of 1,1,3-triaryl-2-azaallyl anions with aryl chlorides is described. The palladium-NIXANTPHOS-based catalyst affords diarylmethylamine derivatives in good yield and without product isomerization. A gram scale sequential one-pot ketimine synthesis/arylation protocol was also developed.
Synthesis of diarylmethylamines via palladium-catalyzed regioselective arylation of 1,1,3-triaryl-2-azaallyl anions
Li, Minyan,Yuecel, Baris,Adrio, Javier,Bellomo, Ana,Walsh, Patrick J.
, p. 2383 - 2391 (2014/05/20)
Diarylmethylamines are of great interest due to their prevalence in pharmaceutical chemistry. As a result, new methods for their synthesis are in demand. Herein, we report a versatile protocol for the synthesis of diarylmethylamine derivatives involving palladium-catalyzed arylation of in situ generated 2-azaallyl anion intermediates. The 2-azaallyl anions are generated by reversible deprotonation of readily available aldimine and ketimine precursors. Importantly, the arylated aldimine and ketimine products do not undergo isomerization under the reaction conditions. Scale-up of the arylation and hydrolysis of the resulting products to furnish diarylmethylamines were also successfully performed. This journal is the Partner Organisations 2014.
Carbon-carbon bond formations at the benzylic positions of N-benzylxanthone imines and N-benzyldi-1-naphthyl ketone imine
Niwa, Takashi,Suehiro, Takafumi,Yorimitsu, Hideki,Oshima, Koichiro
experimental part, p. 5125 - 5131 (2009/11/30)
Two N-benzyl imines are designed to allow for carbon-carbon bond formations at the aminated benzylic positions. Direct benzylic arylation reactions of N-benzylxanthone imine with aryl chlorides proceed under palladium catalysis in the presence of cesium hydroxide, yielding the corresponding benzhydrylamine derivatives. Alkylation reactions of N-benzyldi-1-naphthyl ketone imine with alkyl halides in the presence of potassium tert-butoxide afford the corresponding 1-phenylalkylamines in high yields. Conjugate addition of N-benzyldi-1-naphthyl ketone imine is also described.
