Hydrogen bond mediated conversion of benzenenitriles and arylacetonitriles to amides: an “on/in-water” reaction strategy

Choudhury, Shubhranshu Shekhar; Mahapatra, Shivam; Biswal, Himansu S.

doi:10.1039/d2gc01341j

Cited by 10 publications

(20 citation statements)

References 61 publications

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“…The possibility of employing choline hydroxide (ChOH) as an alternative catalyst was explored. Some of our recent works with ChOH and the promising results obtained , further motivated us to optimize the reaction conditions as shown in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Choline hydroxide (ChOH) can be used for hydrogen-bond-assisted catalysis. , The DFT studies were performed to propose a plausible reaction mechanism for the Claisen–Schmidt condensation between nucleophilic acetone and an electrophilic aromatic aldehyde with the ChOH catalyst. DFT calculations were performed, taking benzaldehyde as the model substrate.…”

Section: Resultsmentioning

confidence: 99%

“…Considering the significance of this synthesis strategy, several catalysts with certain desirable characteristics have been developed to date. 38−40 Even today, extensive research is being performed to Previous reports on synthesizing 1,8-naphthyridines 68 and aromatic and arylbenzene amides 69 demonstrated that ChOH could catalyze these reactions with remarkable efficiency even in moderate conditions. Thus, we started our optimization with 1 mol % ChOH at room temperature (Table 1, entry 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Previous reports on synthesizing 1,8-naphthyridines 68 and aromatic and arylbenzene amides 69 demonstrated that ChOH could catalyze these reactions with remarkable efficiency even in moderate conditions. Thus, we started our optimization with 1 mol % ChOH at room temperature (Table 1, entry 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…70 In addition, computational studies can also provide information on how different types of noncovalent interactions modulate the catalytic reaction pathways. 68,69,75,76 Since this reaction happens in water, and the catalyst possesses hydrogen bonding sites, it is expected that hydrogen bonding has an important role in this catalytic reaction. Herein, we have designed a synthesis strategy for the ChOHassisted coupling of nucleophilic acetone with an electrophilic aromatic aldehyde to produce α,β-unsaturated ketones.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis of α,β-Unsaturated Ketones in Water: The Claisen–Schmidt Condensation Revisited

Choudhury

Mahapatra

Sahu

et al. 2022

ACS Sustainable Chem. Eng.

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Carrying out organic synthesis in an aqueous medium is always challenging. Herein, we present a highly efficient method for the synthesis of α,β-unsaturated ketones in water through the Claisen−Schmidt condensation by using a green catalyst, choline hydroxide (ChOH). The products were isolated without any chromatographic separation technique. The catalyst shows high substrate tolerance and works well with electrondonating and electron-withdrawing substituted aromatic aldehydes. Not only is the catalyst metal-free and nontoxic, but it also offers the advantage of forming strong hydrogen bonds with the transition state and intermediates, facilitating the reaction and enhancing the product yield. A variety of substrate scopes has been explored. The catalysis happens at 50 °C in water which is the significant finding of this study. The reaction mechanism of this hydrogen-bond-mediated catalysis was thoroughly investigated with density functional theory (DFT). The plausible reaction pathway was proposed based on the energetics of the reactants, intermediates, transition states, and product. Further, quantum theory of atoms in molecules (QTAIM) and noncovalent interactions (NCI) index analyses were done to demonstrate the effects of strong hydrogen bonds in the crucial steps of the reaction pathway. The obtained results correlate well with our hypothesis and validate our proposed mechanism, suggesting that the hydrogen-bond-mediated catalysis needs special attention in carrying out organic synthesis in water.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis of α,β-Unsaturated Ketones in Water: The Claisen–Schmidt Condensation Revisited

Choudhury

Mahapatra

Sahu

et al. 2022

ACS Sustainable Chem. Eng.

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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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A Co‐Ni‐CM Heterogeneous Catalyst for the Direct Synthesis of Amides from the Oxidative Coupling of Aldehydes with N‐Substituted Formamides

Huang

Sun

et al. 2023

ChemCatChem

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Given the importance of amides in pharmaceutical and chemical industries, a Co−Ni composites (Co−Ni‐CM) heterogeneous catalytic system for the synthesis of amides from the oxidative coupling of aldehydes with N‐substituted formamides has been developed under mild conditions. The catalyst was prepared by pyrolysis under ambient atmosphere using Co‐BTC supported NiCl2 as a precursor. The catalytic system possesses good catalytic ability and good compatibility with functional groups. The surface morphology and internal element composition of the catalyst were characterized by powder X‐ray diffraction (XRD), BET adsorption, high resolution transmission electron microscope (HRTEM), scanning electron microscope (SEM), inductively coupled plasma emission spectroscopy (ICP‐OES) and X‐ray photoelectron spectroscopy (XPS). The results show that the interaction of Co−Ni is a key factor for the good catalytic activity of the catalyst. Then control experiments related to the mechanism of this transformation indicate a free radical process is involved in this transformation. More importantly, the catalyst has an excellent recycling performance and can be recycled seven times without obvious loss of catalytic activity.

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Hydrogen bond mediated conversion of benzenenitriles and arylacetonitriles to amides: an “on/in-water” reaction strategy

Abstract: Owing to the myriad applications that amides have, hydration of nitriles has emerged as one of the most preferred atom-efficient synthesis methods. Being kinetically slow, this strategy requires some efficient...

Cited by 10 publications

References 61 publications

Synthesis of α,β-Unsaturated Ketones in Water: The Claisen–Schmidt Condensation Revisited

Synthesis of α,β-Unsaturated Ketones in Water: The Claisen–Schmidt Condensation Revisited

Contemporary Approaches for Amide Bond Formation

A Co‐Ni‐CM Heterogeneous Catalyst for the Direct Synthesis of Amides from the Oxidative Coupling of Aldehydes with N‐Substituted Formamides

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