937-24-6Relevant articles and documents
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.
Access to Branched Allylarenes via Rhodium(III)-Catalyzed C-H Allylation of (Hetero)arenes with 2-Methylidenetrimethylene Carbonate
Zhang, Shang-Shi,Zheng, Yi-Chuan,Zhang, Zi-Wu,Chen, Shao-Yong,Xie, Hui,Shu, Bing,Song, Jia-Lin,Liu, Yan-Zhi,Zeng, Yao-Fu,Zhang, Luyong
supporting information, p. 5719 - 5723 (2021/08/16)
A rhodium(III)-catalyzed C-H allylation of (hetero)arenes by using 2-methylidenetrimethylene carbonate as an efficient allylic source has been developed for the first time. Five different directing groups including oxime, N-nitroso, purine, pyridine, and pyrimidine were compatible, delivering various branched allylarenes bearing an allylic hydroxyl group in moderate to excellent yields.
Three-Component Couplings among Heteroarenes, Difluorocyclopropenes, and Water via C-H Activation
Liu, Xuexin,Chen, Jian,Yang, Chunyan,Wu, Zhouping,Li, Zhiyang,Shi, Yuesen,Huang, Tianle,Yang, Zhongzhen,Wu, Yong
supporting information, p. 6831 - 6835 (2021/09/08)
Three-component couplings have been realized for efficiently constructing various nitrogen-containing skeletons via C-H activation, where difluorocyclopropenes have been first identified as coupling partners. Many substrates including sp2 and sp3 C-H substrates were well tolerated, furnishing the corresponding products in good yields. Furthermore, a catalyst-dependent reaction was also developed, enabling divergent construction of two different frameworks. The application value of these reactions was demonstrated in gram-scale experiments with as little as 1 mol % catalyst.
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.
Rh(iii)-catalyzed, hydrazine-directed C-H functionalization with 1-alkynylcyclobutanols: A new strategy for 1: H -indazoles
Zhang, Lei,Chen, Junyu,Chen, Xiahe,Zheng, Xiangyun,Zhou, Jian,Zhong, Tianshuo,Chen, Zhiwei,Yang, Yun-Fang,Jiang, Xinpeng,She, Yuan-Bin,Yu, Chuanming
supporting information, p. 7415 - 7418 (2020/07/15)
Rh(iii)-catalyzed coupling of phenylhydrazines with 1-alkynylcyclobutanols was realized through a hydrazine-directed C-H functionalization pathway. This [4+1] annulation, based on the cleavage of a Csp-Csp triple bond in alkynylcyclobutanol, provides a new pathway to prepare diverse 1H-indazoles under mild reaction conditions. This journal is
Rhodium(iii)-catalyzed indole synthesis at room temperature using the transient oxidizing directing group strategy
Shang, Yaping,Jonnada, Krishna,Yedage, Subhash Laxman,Tu, Hua,Zhang, Xiaofeng,Lou, Xin,Huang, Shijun,Su, Weiping
supporting information, p. 9547 - 9550 (2019/08/15)
Rh-catalyzed reactions of N-alkyl anilines with internal alkynes at room temperature have been developed using an in situ generated N-nitroso group as a transient oxidizing directing group. Due to mild reaction conditions, this method enabled synthesis of a broad range of N-alkyl indoles, including even two indole-based medicinal compounds. Our work disclosed the feasibility of the transient oxidizing directing group strategy in C-H functionalization reactions, which possesses the potential to enhance overall step-economy and impart new reactivity patterns to substrates.
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.
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.
