Manganese-mediated reductive amidation of esters with nitroarenes

Cheung, Chi Wai; Shen, Ni; Wang, Shao-Peng; Ullah, Asim; Hu, Xile; Ma, Jun‐An

doi:10.1039/c8qo01405a

Cited by 45 publications

(37 citation statements)

References 51 publications

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“…Our interest in the development of cost-effective strategy to form amide bonds stems from the consideration of its potential utility in accessing valuable motifs. [31][32][33][34] To avoid the synthesis and purification of reactive metal catalysts, we commenced our studies by using commercially available metal salts as precatalysts for the amidation of ethyl benzoate (1a) with aniline (2a). With our endeavor in the exploration of Cr-catalyzed crosscoupling reactions, 35 we speculated that a reactive low-valent Cr, being formed in situ by reduction with Mg, 36,37 benign CrCl 2 salt was chose as pre-catalyst by the treatment with magnesium in the amidation (Table 1).…”

Section: Resultsmentioning

confidence: 99%

Chromium-Catalyzed Ligand-Free Amidation of Esters with Anilines

Chen

Ling

Luo

et al. 2020

Bulletin of the Chemical Society of Japan

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Advance Publication is a service for online publication of manuscripts prior to releasing fully edited, printed versions. Entire manuscripts and a portion of the graphical abstract can be released on the web as soon as the submission is accepted. Note that the Chemical Society of Japan bears no responsibility for issues resulting from the use of information taken from unedited, Advance Publication manuscripts.

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Section: Resultsmentioning

confidence: 99%

Chromium-Catalyzed Ligand-Free Amidation of Esters with Anilines

Chen

Ling

Luo

et al. 2020

Bulletin of the Chemical Society of Japan

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“…Thereafter, Cheung and Ma and co-workers reported amidation of aliphatic and aromatic esters 132 with nitroarenes 1 using Mn powder and TMSCl in the absence of any additional ligands or catalyst for preparing amides 133 (Scheme 48). [44] Based on mechanistic study they suggested nitrosobenzene 134 as the possible intermediate participating in the amidation reaction (Scheme 49). TMSCl was essentially required in the process for removing the oxide from surface of Mn and activate the catalyst concomitantly for deoxygenating the nitroarenes.…”

Section: Amidation Of Estersmentioning

confidence: 99%

Direct Access to Amides from Nitro‐Compounds via Aminocarbonylation and Amidation Reactions: A Minireview

Barak

Batra

2021

The Chemical Record

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The ubiquity of the amide bond in functional molecules including proteins, natural products, pharmaceuticals, agrochemicals and materials provides impetus to design and develop newer strategies for the generation of this linkage. Owing to growing awareness about sustainability and development of benign strategies, the traditional route of synthesis of amides via reaction between carboxylic acids and amines in the presence of stoichiometric amount of coupling reagents is tagged to be harsh and wasteful. In one of the unconventional routes, nitro compounds are used directly as amine surrogates for preparing amides mostly via aminocarbonylation and amidation reactions. Typically, such processes involves nitroarenes owing to their propensity to transform into nitroso, hydroxylamine, diazo, hydrazine or aniline intermediates in situ under the influence of suitable catalyst or oxidant. This short review provides the comprehensive overview of these reactions including insight into the scope and their mechanisms.

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“…In 2019, Cheung, Ma, and co-workers reported the Mnmediated reductive amidation of alkyl and aryl esters with nitroarenes in the absence of additional catalysts or ligands (Scheme 42). 67 In this approach, they only need TMSCl as additive to reductively couple nitroarenes using Mn as reductant in DMA at 120 °C. This reductive amidation is characterized by a broad substrate scope with respect to both ester and nitroarene partners.…”

Section: Syn Thesismentioning

confidence: 99%

Non-Classical Amide Bond Formation: Transamidation and Amidation of Activated Amides and Esters by Selective N–C/O–C Cleavage

Szostak

2020

Synthesis

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In the past several years, tremendous advances have been made in non-classical routes for amide bond formation that involve transamidation and amidation reactions of activated amides and esters. These new methods enable the formation of extremely valuable amide bonds via transition-metal-catalyzed, transition-metal-free, or metal-free pathways by exploiting chemoselective acyl C–X (X = N, O) cleavage under mild conditions. In a broadest sense, these reactions overcome the formidable challenge of activating C–N/C–O bonds of amides or esters by rationally tackling nN → π*C=O delocalization in amides and nO → π*C=O donation in esters. In this account, we summarize the recent remarkable advances in the development of new methods for the synthesis of amides with a focus on (1) transition-metal/NHC-catalyzed C–N/C–O bond activation, (2) transition-metal-free highly selective cleavage of C–N/C–O bonds, (3) the development of new acyl-transfer reagents, and (4) other emerging methods.1 Introduction2 Transamidation of Amides2.1 Transamidation by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)2.2 Transition-Metal-Free Transamidation via Tetrahedral Intermediates2.3 Reductive Transamidation2.4 New Acyl-Transfer Reagents2.5 Tandem Transamidations3 Amidation of Esters3.1 Amidation of Esters by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)3.2 Transition-Metal-Free Amidation of Esters via Tetrahedral Intermediates3.3 Reductive Amidation of Esters4 Transamidations of Amides by Other Mechanisms5 Conclusions and Outlook

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Manganese-mediated reductive amidation of esters with nitroarenes

Abstract: N-Aryl amides were synthesized via the manganese-mediated amidation of esters with nitroarenes without the need for additional catalysts or ligands.

Cited by 45 publications

References 51 publications

Chromium-Catalyzed Ligand-Free Amidation of Esters with Anilines

Chromium-Catalyzed Ligand-Free Amidation of Esters with Anilines

Direct Access to Amides from Nitro‐Compounds via Aminocarbonylation and Amidation Reactions: A Minireview

Non-Classical Amide Bond Formation: Transamidation and Amidation of Activated Amides and Esters by Selective N–C/O–C Cleavage

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