Rhodium(III)‐Catalyzed Directed C−H Amidation of <i>N</i>‐Nitrosoanilines and Subsequent Formation of 1,2‐Disubstituted Benzimidazoles

Chen, Yanyu; Zhang, Rong; Peng, Qiujun; Xu, Liang; Pan, Xuebiao

doi:10.1002/asia.201701287

Cited by 26 publications

(8 citation statements)

References 91 publications

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“…The optimized reaction conditions employing 3 mol% Rh(III), 12 mol% AgSbF 6 , and 15 mol% NaOAc in n ‐heptane gave a variety of ortho ‐amidated nitrosoanilines (Scheme 19). [24] This study demonstrated that N ‐nitrosoanilines bearing EDGs and EWGs smoothly and gratifyingly promoted the reaction in the presence of aryl‐ or alkyl‐ substituted dioxazolones, regardless of their electronic properties, to give the target product in excellent yield. Later, Chen and co‐workers developed the C−H amidation of N ‐nitrosoanilines using 1,4,2‐dioxazol‐5‐ones under ball‐milling conditions.…”

Section: Rhodium‐catalyzed C−h Functionalizationmentioning

confidence: 76%

Recent Advances and Strategies for the Transition‐Metal‐Catalyzed C−H Functionalization of N‐Nitrosoanilines

et al. 2021

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The challenges faced in the activation and functionalization of C−H bonds while producing high‐value aromatic intermediates are significant for synthetic organic chemistry. This review summarizes the advancements made toward the C−H functionalization of N‐nitrosoanilines in the past decade, in which the nitroso group coordinates to a transition metal, such as rhodium, palladium, cobalt, iridium, and ruthenium, acting as a directing group to allow the activation of the ortho C−H bond. The versatility of this synthetic approach has led to the regio‐ and chemoselective introduction of various functional groups giving rise to aromatic congeners with diverse functional and structural properties. C−H functionalized nitroso compounds can be further transformed into valuable synthetic intermediates and unique heterocyclic compounds. A description of the mechanism underlying each reaction is also included. This review includes the following sections:

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Section: Rhodium‐catalyzed C−h Functionalizationmentioning

confidence: 76%

Recent Advances and Strategies for the Transition‐Metal‐Catalyzed C−H Functionalization of N‐Nitrosoanilines

et al. 2021

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“…Rh(III)-Catalyzed ortho-amidation of Nnitrosoaniline was performed using 1,4,2-dioxazol-5-ones as an amidating agent in presence of AgSbF 6 (12 mol%) and NaOAc (15 mol%) in n-heptane (Scheme 16, Condition A). [45] This protocol facilitated the synthesis of a series of benzamides with both electron-donating and -withdrawing substituents in moderate to good yields. The reaction is irreversible as no deuterium incorporated product was isolated from the control experiment using CD 3 OD under standard condition.…”

Section: Carbonà Nitrogen Bond Formationmentioning

confidence: 99%

“…An efficient ortho ‐amidation of N ‐nitrosoanilines was developed by Pan group in 2017. Rh(III)‐Catalyzed ortho ‐amidation of N ‐nitrosoaniline was performed using 1,4,2‐dioxazol‐5‐ones as an amidating agent in presence of AgSbF 6 (12 mol%) and NaOAc (15 mol%) in n ‐heptane (Scheme 16, Condition A) [45] . This protocol facilitated the synthesis of a series of benzamides with both electron‐donating and ‐withdrawing substituents in moderate to good yields.…”

Section: Carbon−nitrogen Bond Formationmentioning

confidence: 99%

N‐Nitroso As A Novel Directing Group in Transition‐Metal‐Catalyzed C(sp²)−H Bond Functionalizations of N‐Nitrosoanilines

2021

Asian J Org Chem

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In the last few decades, the syntheses of bioactive natural products and functional materials have been achieved via CÀ H bond functionalizations where the transition metals in coordination with the directing groups trigger the CÀ H bond activation. A wide variety of directing groups has been recognized for transition-metal-catalyzed ortho-CÀ H bond functionalization of arenes. Recently, N-nitroso group has been established as a new, efficient and sometimes as a traceless directing group in ortho-C(sp 2 )À H bond functionali-zations of N-nitrosoanilines. During functioning as a tracelessdirecting-group, the N -O bond of N-nitrosoaniline acts as an internal oxidant to recycle the employed catalyst. Pd, Rh, Co, Ru and Ir catalysts have been screened for the ortho CÀ H bond functionalizations of N-nitrosoanilines constructing new CÀ C, CÀ O, CÀ N and CÀ X bonds. Herein, we have summarized all the recently developed N-nitroso group directed ortho-C(sp 2 )À H bond functionalization reactions of N-nitrosoanilines.

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“…For the activation of aniline derivatives a nitroso 74 or a pyrimidyl group 77 can be used as a DG. Pan et al [31a] . used nitroso as a DG for N ‐alkyl anilines to get amidation products 75 with dioxazolones 7 (Scheme 26a).…”

Section: Cp*rh(iii)‐catalyzed Directed Ortho Sp2(c)−h Amidation or Ammentioning

confidence: 99%

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp² C−H Activation

Bera

Suchand

et al. 2020

Asian J Org Chem

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The presence of nitrogen atom in a wide variety of organic compounds called for the use of powerful CÀ H activation strategy in the CÀ N bond formation. Pentamethylcyclopentadienyl (Cp*) based, high-valent, group 9 transition-metal complexes have shown a great potential as catalysts in the CÀ H activation/functionalization over the years. This minireview summarizes recent progress made in the context of CÀ N bond formation via catalytic (sp 2)CÀ H activation with Cp*M(III) (M = Co, Rh and Ir) catalysts. A general plausible mechanism is briefly discussed at the beginning, and then results are arranged according to metal cobalt, rhodium and iridium, respectively.

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Rhodium(III)‐Catalyzed Directed C−H Amidation of N‐Nitrosoanilines and Subsequent Formation of 1,2‐Disubstituted Benzimidazoles

Cited by 26 publications

References 91 publications

Recent Advances and Strategies for the Transition‐Metal‐Catalyzed C−H Functionalization of N‐Nitrosoanilines

Recent Advances and Strategies for the Transition‐Metal‐Catalyzed C−H Functionalization of N‐Nitrosoanilines

N‐Nitroso As A Novel Directing Group in Transition‐Metal‐Catalyzed C(sp²)−H Bond Functionalizations of N‐Nitrosoanilines

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp² C−H Activation

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Rhodium(III)‐Catalyzed Directed C−H Amidation of N‐Nitrosoanilines and Subsequent Formation of 1,2‐Disubstituted Benzimidazoles

Cited by 26 publications

References 91 publications

Recent Advances and Strategies for the Transition‐Metal‐Catalyzed C−H Functionalization of N‐Nitrosoanilines

Recent Advances and Strategies for the Transition‐Metal‐Catalyzed C−H Functionalization of N‐Nitrosoanilines

N‐Nitroso As A Novel Directing Group in Transition‐Metal‐Catalyzed C(sp2)−H Bond Functionalizations of N‐Nitrosoanilines

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp2 C−H Activation

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N‐Nitroso As A Novel Directing Group in Transition‐Metal‐Catalyzed C(sp²)−H Bond Functionalizations of N‐Nitrosoanilines

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp² C−H Activation