6330-55-8Relevant academic research and scientific papers
One-Pot Tandem ortho-Naphthoquinone-Catalyzed Aerobic Nitrosation of N-Alkylanilines and Rh(III)-Catalyzed C-H Functionalization Sequence to Indole and Aniline Derivatives
Si, Tengda,Kim, Hun Young,Oh, Kyungsoo
, p. 1152 - 1163 (2021/01/14)
The nitroso group served as a traceless directing group for the C-H functionalization of N-alkylanilines, ultimately removed after functioning either as an internal oxidant or under subsequent reducing conditions. The unique ability of o-NQ catalysts to aerobically oxidize the N-alkylanilines without using solvents and stoichiometric amounts of oxidants has rendered the new opportunity to develop the telescoped catalyst systems without a need for directly handling the hazardous N-nitroso compounds.
Rhodium-catalyzed tandem acylmethylation/annulation ofN-nitrosoanilines with sulfoxonium ylides for the synthesis of substituted indazoleN-oxides
Cui, Xin-F,Huang, Guo-Sh
supporting information, p. 4014 - 4018 (2020/06/09)
An atom-economical protocol for synthesizing indazoleN-oxides from readily availableN-nitrosoanilines and sulfoxonium ylides through the rhodium(iii)-catalyzed C-H activation and cyclization reaction is described here. This protocol employs nitroso as a traceless directing group. The transformation features powerful reactivity, tolerates various functional groups, and proceeds with moderate to good yields under an ambient atmosphere, providing a straightforward approach to access structurally diverse and valuable indazoleN-oxide derivatives. Importantly, this new annulation process represents a hitherto unobserved reactivity pattern for theN-nitroso group.
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
supporting information, 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.
Rhodium-catalyzed oxidative C-H/C-H cross-coupling of aniline with heteroarene: N-nitroso group enabled mild conditions
He, Shuang,Tan, Guangying,Luo, Anping,You, Jingsong
supporting information, p. 7794 - 7797 (2018/07/25)
The development of transition metal-catalyzed oxidative C-H/C-H cross-coupling between two (hetero)arenes to forge aryl-heteroaryl motifs under mild conditions is an appealing yet challenging task. Herein, we disclose a rhodium-catalyzed oxidative C-H/C-H cross-coupling reaction of an N-nitrosoaniline with a heteroarene under mild conditions. The judicious choice of the N-nitroso group as a directing group enables heightened reactivity. The coupled products could be transformed expediently to (2-aminophenyl)heteroaryl skeletons.
Rhodium(III)-Catalyzed Directed C?H Amidation of N-Nitrosoanilines and Subsequent Formation of 1,2-Disubstituted Benzimidazoles
Chen, Yanyu,Zhang, Rong,Peng, Qiujun,Xu, Lanting,Pan, XianHua
supporting information, p. 2804 - 2808 (2017/10/20)
An efficient rhodium-catalyzed direct C?H amidation of N-nitrosoanilines with 1,4,2-dioxazol-5-ones as amidating agents has been developed. This method featured mild reaction conditions, a wide substrate scope and satisfactory yields. Besides, the amidated products could be readily converted to pharmaceutically valuable 1,2-disubstituted benzimidazoles via an HCl-mediated deprotection/cyclization process in one pot.
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.
