17576-86-2Relevant academic research and scientific papers
Cp?Rh(iii) catalyzed: Ortho -halogenation of N -nitrosoanilines by solvent-controlled regioselective C-H functionalization
Peng, Qiujun,Hu, Jian,Huo, Jiyou,Yuan, Hongshun,Xu, Lanting,Pan, Xianhua
, p. 4471 - 4481 (2018/06/29)
We present a novel, efficient, and regioselective method for the rhodium-catalyzed direct C-H ortho-halogenation of anilines that involves a removable N-nitroso directing group. This method featured mild reaction conditions, wide substrate scope, good functional group tolerance and satisfactory yields. To maintain the high ortho-regioselectivity and conversion, increasing the steric hindrance of the solvent was critical. Preliminary mechanistic studies suggest that C-H activation may be involved in the rate-determining step.
Highly selective sp3 C-N bond activation of tertiary anilines modulated by steric and thermodynamic factors
Jia, Xiaodong,Li, Pengfei,Shao, Yu,Yuan, Yu,Ji, Honghe,Hou, Wentao,Liu, Xiaofei,Zhang, Xuewen
supporting information, p. 5568 - 5574 (2017/12/06)
A highly selective sp3 C-N cleavage of tertiary anilines was achieved using the TBN/TEMPO catalyst system. When N,N-diaklylanilines (alkyl, benzyl) were employed, the N-CH3 bond was selectively cleaved via radical C-H activation. Moreover, when the allyl group was installed, totally reverse selectivity was observed. It is worth noting that the solvent effect is also crucial to obtain high reaction efficiency and selectivity.
Rhodium(III)-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate for cycloaddition/fragmentation synthesis of indazoles
Chen, Jinsen,Chen, Pei,Song, Chao,Zhu, Jin
supporting information, p. 14245 - 14249 (2015/02/05)
RhIII-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N-nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C-H functionalization-based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tri-cyclic-fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.
