Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines

Yin, Jianchuan; Zhang, Jingyu; Cai, Changqun; Deng, Guo‐Jun; Gong, Hang

doi:10.1021/acs.orglett.8b03542

Cited by 57 publications

(33 citation statements)

References 106 publications

(26 reference statements)

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“…Even ionic liquid [21] and catalyst‐free transamidation of aromatic amines with DMF could be conducted (Figure 1). [22] Nevertheless, drawbacks such as co‐catalyst, solvent and large excess catalysts were inevitable in most strategies.…”

Section: Figurementioning

confidence: 99%

Organophosphoric Acid Promoted Transamidation: Using N,N‐Dimethylformamide and N,N‐Dimethylacetamide as the Acyl Sources

Jiang

Chen

et al. 2021

ChemistrySelect

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A new and efficient protocol for the transamidation promoted by organophosphoric acid has been reported. The protocol was applied for the N‐formylation of amines including aromatic, aliphatic and heterocyclic amines, affording moderate to excellent yields (54‐98 %) via the transamidation of N,N‐dimethylformamide (DMF). Similarly, the protocol was used for the N‐acylation of a range of amines, moderate yields via transamidation of N,N‐dimethylacetamide (DMA) were obtained. Moreover, the protocol could be easily performed on a multigram scale.

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Section: Figurementioning

confidence: 99%

Organophosphoric Acid Promoted Transamidation: Using N,N‐Dimethylformamide and N,N‐Dimethylacetamide as the Acyl Sources

Jiang

Chen

et al. 2021

ChemistrySelect

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“…Gong and co-workers extended this procedure to a variety of aliphatic primary amides and weakly nucleophilic aromatic amines under heating at 150°C (Scheme 25, B). 57 Our group has developed substrate self-promoted transamidations for the simple and green synthesis of glycolipids and glycoconjugates. Under solvent-free conditions, unprotected glycosyl carboxamides of type 154 were converted into secondary and tertiary amides, using amines 156-161, in good to excellent yields (68-95%).…”

Section: Scheme 24 Solvent-promoted Transamidation Reactions 55mentioning

confidence: 99%

“…Amine self-promoted transamidations56,57 -and solvent-free formylation of amine in the group of Legros. -and solvent-free amidation of amine in the group of Gong.…”

mentioning

confidence: 99%

Amide Synthesis by Transamidation of Primary Carboxamides

Marković

2020

Synthesis

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The amide functionality is one of the most important and widely used groups in nature and in medicinal and industrial chemistry. Because of its importance and as the actual synthetic methods suffer from major drawbacks, such as the use of a stoichiometric amount of an activating agent, epimerization and low atom economy, the development of new and efficient amide bond forming reactions is needed. A number of greener and more effective strategies have been studied and developed. The transamidation of primary amides is particularly attractive in terms of atom economy and as ammonia is the single byproduct. This review summarizes the advancements in metal-catalyzed and organocatalyzed transamidation methods. Lewis and Brønsted acid transamidation catalysts are reviewed as a separate group. The activation of primary amides by promoter, as well as catalyst- and promoter-free protocols, are also described. The proposed mechanisms and key intermediates of the depicted transamidation reactions are shown.1 Introduction2 Metal-Catalyzed Transamidations3 Organocatalyzed Transamidations4 Lewis and Brønsted Acid Catalysis5 Promoted Transamidation of Primary Amides6 Catalyst- and Promoter-Free Protocols7 Conclusion

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“…Generally, the preparation of amide involves hydroamination of alkynes (Uenoyama et al, 2005;Valeur and Bradley et al, 2009), hydration of nitriles (Goto et al,2008;Raman et al, 2009;Williams et al, 2011) and the coupling of carboxylic acids, aldehydes and alcohols with amines (Srinivas and Das, 2003;Hosseini-Sarvari and Sharghi et al, 2006;Gunanathan andMilstein, 2007, Milstein, 2011;Nordstrom et al, 2008;Arnold et al, 2008;Zweifel et al, 2009;Watson et al, 2009;Soule et al, 2011;Lundberg et al, 2012;Gosh et al, 2012;Yamaguchi et al, 2012). Additionally, transamidation is a convenient and straightforward method for exchanging the constituents of two different amide groups and some significant progress has been achieved in recent years (Eldred et al, 2003;Eldred et al, 2008;Nguyen et al, 2012, Allen et al, 2012Zhang et al, 2012;Nageswara et al, 2014;Becerra-Figueroa et al 2014;Garg et al 2017;Yin et al, 2019;Ghosh et al, 2019). Chitin possesses enormous N-acetyl groups and can be recognized as a kind of renewable amide compounds.…”

Section: Introductionmentioning

confidence: 99%

Selective Utilization of N-acetyl Groups in Chitin for Transamidation of Amines

Shen

Liu

et al. 2021

Front. Chem. Eng.

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The selective transformation of chitin into various renewable N-containing chemicals and medicines has attracted increasing attention. However, the N-acetyl groups in chitin construct strong hydrogen bond networks, which restricts its depolymerization and transformation. The selective conversion of robust chitin commonly requires considerable base catalysts to remove the N-acetyl group as a byproduct in advance, which is non-compliance with the principle of atomic economy. Herein, for the first time we demonstrate a novel approach to achieve the selective utilization of the N-acetyl group in chitin for transamidation of chitin with amines. A series of amine derivatives, mainly including aliphatic amine, cyclic amine and functionalized aromatic amine, could be selectively converted into the corresponding amide products frequently found in pharmaceuticals. Furthermore, the solid residue after removing the acetyl group (denoted as De-chitin) with the sufficient exposure of -NH2 groups as a solid base catalyst shows excellent performance in the aldol condensation reaction of furfural and acetone to produce fuel precursors. Our process provides a strategy that exploiting every functional group adequately in substrates to obtain value-added chemicals.

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Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines

Cited by 57 publications

References 106 publications

Organophosphoric Acid Promoted Transamidation: Using N,N‐Dimethylformamide and N,N‐Dimethylacetamide as the Acyl Sources

Organophosphoric Acid Promoted Transamidation: Using N,N‐Dimethylformamide and N,N‐Dimethylacetamide as the Acyl Sources

Amide Synthesis by Transamidation of Primary Carboxamides

Selective Utilization of N-acetyl Groups in Chitin for Transamidation of Amines

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