Direct <i>N</i>-formylation of nitroarenes with CO<sub>2</sub>

Shen, Ni; Zhai, Shi‐Jing; Cheung, Chi Wai; Ma, Jun‐An

doi:10.1039/d0cc03098h

Cited by 25 publications

(9 citation statements)

References 64 publications

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“…Their success encompasses the synthesis of aliphatic, [199] aromatic [200] and unsaturated amides, along with unsaturated lactams [201] . Standard aromatic amides have been obtained using Mo(CO) 6 (by Wu [202] ) or CO (by Ma [203] ), employing varied catalytic systems. This strategy has also been extended to the preparation of oxindoles [204] and quinazolinones [205] .…”

Section: Construction Of C=o Bondmentioning

confidence: 99%

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Contemporary Approaches for Amide Bond Formation

Acosta‐Guzmán,

Ojeda‐Porras,

Gamba‐Sánchez

2023

Adv Synth Catal

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Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out of the thirty‐seven new drugs approved by the FDA in 2022, eleven are small molecules containing at least one amide bond. Additionally, there are nineteen large molecules approved as new drugs, some of which have peptide structures, and therefore, also bear amide bonds. In recent years, multiple teams have embraced the challenge of developing more efficient methods for amide bond formation. This dedication has led to numerous publications appearing monthly in prestigious journals, showcasing significant advancements in this field. The primary goal of this review is to present the most viable strategies for constructing the amide bond. It is crucial to differentiate between amide bond formation and amide synthesis; hence, the focus is on describing specific methods for forming new C(O)−N bonds. In particular, this review concentrates on the methods developed within the last six years. There is a particular emphasis on new approaches that consider the thought process when selecting the starting materials and functional groups. This approach ensures coverage of all the most common chemical transformations that yield new amide bonds.

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Section: Construction Of C=o Bondmentioning

confidence: 99%

“…This strategy has also been extended to the preparation of oxindoles [204] and quinazolinones [205] . Additionally, Ma and co‐workers [203] introduced a unique utilization of CO as the carbon source in a reductive protocol for nitro compound formylation (depicted in Figure 43).…”

Section: Construction Of C=o Bondmentioning

confidence: 99%

Contemporary Approaches for Amide Bond Formation

Acosta‐Guzmán,

Ojeda‐Porras,

Gamba‐Sánchez

2023

Adv Synth Catal

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“…21–26 In addition, amides have been obtained from reactions between nitroarenes and aryl halides (or equivalent) in the presence of a carbonyl source, and in most cases, nickel was employed as the catalyst of choice. 27 28 29 Although nickel offers a more sustainable option, the general superior robustness of palladium catalysts in cross-coupling reactions prompted us to explore herein an optimisation study for a palladium-catalysed reductive aminocarbonylation of aryl halides with nitroarenes and a subsequent application of the protocol in the synthesis of a variety of amides. 30…”

Section: Table 1 Optimisation Study For the Reductive A...mentioning

confidence: 99%

Palladium-Catalysed Reductive Aminocarbonylation of Aryl Bromides and Iodides with Nitroarenes

Moshapo¹,

Mkhonazi²,

Mabila³

2022

SynOpen

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Amide functional groups are a structural feature in a vast array of beneficial organic molecules. This has resulted in a surge in new methodologies developed to enable access to this functional group using a broad range of coupling partners. Herein, we report a palladium-catalysed reductive aminocarbonylation of aryl bromides and iodides with nitroarenes to afford the respective amide products. The developed protocol employs Mo(CO)6 as a carbonyl source and a combination of Zn and TMSCl as co-reducing agents. For most substrates, the anticipated amide products were obtained in modest to high amide product yields.

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“…Cheung and Ma and co-workers developed a straightforward synthesis of N-aryl formamide 173 via N-formylation of nitroarenes 1 with carbon dioxide in the presence of iron and 1,1,3,3,-tetramethyldisiloxane (TMDSO) (Scheme 68). [58] Based on the control experiments it was suggested that the nitroarene was sequentially reduced to nitrosobenzene, Nphenyl hydroxylamine, azoxybenzene, azobenzene and finally diphenylhydrazine, which participated in the formylation reaction.…”

Section: Amidation With Carbon Dioxidementioning

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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Direct N-formylation of nitroarenes with CO₂

Abstract: Herein we describe a straightforward N-formylation of nitroarenes with CO2 to access N-aryl formamides exclusively in the presence of iron and hydrosilane as additives. This protocol showcases a good tolerance...

Cited by 25 publications

References 64 publications

Contemporary Approaches for Amide Bond Formation

Contemporary Approaches for Amide Bond Formation

Palladium-Catalysed Reductive Aminocarbonylation of Aryl Bromides and Iodides with Nitroarenes

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

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Direct N-formylation of nitroarenes with CO2

Abstract: Herein we describe a straightforward N-formylation of nitroarenes with CO2 to access N-aryl formamides exclusively in the presence of iron and hydrosilane as additives. This protocol showcases a good tolerance...

Cited by 25 publications

References 64 publications

Contemporary Approaches for Amide Bond Formation

Contemporary Approaches for Amide Bond Formation

Palladium-Catalysed Reductive Aminocarbonylation of Aryl Bromides and Iodides with Nitroarenes

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

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Product

Resources

About

Direct N-formylation of nitroarenes with CO₂