- One-Pot Tandem ortho-Naphthoquinone-Catalyzed Aerobic Nitrosation of N-Alkylanilines and Rh(III)-Catalyzed C-H Functionalization Sequence to Indole and Aniline Derivatives
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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.
- Si, Tengda,Kim, Hun Young,Oh, Kyungsoo
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p. 1152 - 1163
(2021/01/14)
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- Divergent C-H activation synthesis of chalcones, quinolones and indoles
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We here report a condition-controlled divergent synthesis strategy of chalcones, quinolones and indoles, which was achieved via a C-H activation reaction of N-nitrosoanilines and cyclopropenones. Variations of Ag salts are observed to be crucial for divergently constructing the three distinct chemical scaffolds. A Rh(i)- and Rh(iii)-cocatalyzed decarbonylation/C-H activation/[3+2] annulation cascade reaction was developed for the synthesis of indoles. These methodologies are characterized by mild reaction conditions, high functional group tolerance, and amenability to gram-scale synthesis, providing a reference for future derivation of new chemical scaffolds by C-H activation.
- Shi, Yuesen,Xing, Huimin,Huang, Tianle,Liu, Xuexin,Chen, Jian,Guo, Xiaoyu,Li, Guo-Bo,Wu, Yong
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supporting information
p. 1585 - 1588
(2020/02/13)
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- Rhodium(iii)-catalyzed indole synthesis at room temperature using the transient oxidizing directing group strategy
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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.
- Shang, Yaping,Jonnada, Krishna,Yedage, Subhash Laxman,Tu, Hua,Zhang, Xiaofeng,Lou, Xin,Huang, Shijun,Su, Weiping
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p. 9547 - 9550
(2019/08/15)
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- Rhodium-catalyzed annulation of tertiary aniline N-oxides to N-alkylindoles: Regioselective C-H activation, oxygen-atom transfer, and N-dealkylative cyclization
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[Cp?RhIII]-catalyzed annulation of tertiary aniline N-oxides with alkynes was reported to achieve the challenging ortho C-H functionalization of tertiary anilines via N-O bond acting as a traceless directing group. More significantly, this system represents the first example which integrates C-H activation, oxygen-atom transfer, and N-dealkylative cyclization in one reaction. This unprecedented coupling reaction has allowed the construction of N-alkylindole derivatives in high efficiency with broad substrate scope and good functional group tolerance.
- Li, Bin,Xu, Hong,Wang, Huanan,Wang, Baiquan
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p. 3856 - 3862
(2016/07/06)
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- Rh(III)-catalyzed chemoselective C-H functionalizations of tertiary aniline: N -oxides with alkynes
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In this work, we report novel Rh(iii)-catalyzed chemoselective functionalizations of tertiary aniline N-oxides with alkynes, including annulation via the sequential C(sp2)-H and C(sp3)-N activation for the formation of N-alkylindoles and an O-atom transfer (OAT) process for the synthesis of acetophenones.
- Huang, Xiaolei,Liang, Wenbo,Shi, Yang,You, Jingsong
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supporting information
p. 6253 - 6256
(2016/05/19)
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- Cationic Cobalt(III) Catalyzed Indole Synthesis: The Regioselective Intermolecular Cyclization of N-Nitrosoanilines and Alkynes
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The unique regioselectivity and reactivity of cobalt(III) in the direct cyclization of N-nitrosoanilines with alkynes for the expedient synthesis of N-substituted indoles is demonstrated. In the presence of a cobalt(III) catalyst, high regioselectivity was observed when using unsymmetrical meta-substituted N-nitrosoanilines. Moreover, internal alkynes bearing electron-deficient groups, which are almost unreactive in the [Cp?RhIII]-catalyzed system, display good reactivity in this transformation.
- Liang, Yujie,Jiao, Ning
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supporting information
p. 4035 - 4039
(2016/03/19)
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- Co(III)-Catalyzed, Internal and Terminal Alkyne-Compatible Synthesis of Indoles
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A Co(III)-catalyzed, internal and terminal alkyne-compatible indole synthesis protocol is reported herein. The N-amino (hydrazine) group imparts distinct, diverse reactivity patterns for directed C-H functionalization/cyclization reactions. Notable synthetic features include regioselectivity for a meta-substituted arylhydrazine, regioselectivity for a chain-branched terminal alkyne, formal incorporation of an acetylenic unit through C2-desilylation on a C2-silylated indole derivative, formal inversion of regioselectivity through consecutive C3-derivatization and C2-desilylation processes, and formal bond migration for a linear-chain terminal alkyne.
- Zhou, Shuguang,Wang, Jinhu,Wang, Lili,Chen, Kehao,Song, Chao,Zhu, Jin
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supporting information
p. 3806 - 3809
(2016/08/16)
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- Rhodium(III)-catalyzed synthesis of indoles from 1-alkylidene-2- arylhydrazines and alkynes via C-H and N-N bond cleavages
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1-Alkylidene-2-arylhydrazines undergo annulative coupling with internal alkynes in the presence of a rhodium(III) catalyst and a copper(II) salt. The reaction proceeds through cleavage of the C-H and N-N bonds of hydrazines to afford 1,2,3-trisubstituted indole derivatives.
- Matsuda, Takanori,Tomaru, Yuki
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supporting information
p. 3302 - 3304
(2014/06/09)
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