Direct synthesis of amides and imines by dehydrogenative homo or cross-coupling of amines and alcohols catalyzed by Cu-MOF

Anbardan, Soheil Zamani; Mokhtari, Javad; Yari, Ahmad Reza; Bozcheloei, Abolfazl Hassani

doi:10.1039/d1ra03142b

Cited by 18 publications

(7 citation statements)

References 74 publications

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“…without oxidation by N 2 O), as already described in the literature with these substrates upon UV irradiation [36] . For cross‐coupling reactions, that afford lower selectivities compared with the homo‐coupling reactions (Table 2), formation of traces of amides was possible, [37] but was not evidenced.…”

Section: Resultsmentioning

confidence: 86%

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

Delaunay,

Denicourt‐Nowicki,

Roucoux

2023

ChemCatChem

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In a climate change context, N2O contributes to global warming with CO2 and CH4. As an inert molecule, its upgrading as oxidant still constitutes a challenge in chemical synthesis. Here, the synthesis of imines was unprecedently performed using nitrous oxide (N2O) as a novel and highly selective oxidative agent for the photocatalytic homo‐coupling of amines. In a similar way, unsymmetric imines were produced through cross‐coupling of amines with alcohols. Promisingly, this greenhouse gas showed excellent performances towards the target reactions when photocatalytically activated at atmospheric pressure, with silver photodeposited on titanium dioxide as catalyst. Relevantly, reactions under N2O atmosphere exhibited high conversion rates and turn‐over frequencies, and higher selectivities than the ones carried out under a dioxygen atmosphere. Mechanisms for both reactions were detailed, showing the release of nitrogen and water as benign by‐products.

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Section: Resultsmentioning

confidence: 86%

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

Delaunay,

Denicourt‐Nowicki,

Roucoux

2023

ChemCatChem

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“…Without losing its catalytic activity, the catalyst ( VIII ) could be recycled and used four times (Scheme 11). [73] A general plausible mechanism for the synthesis N‐aryl and N‐heterocyclic compounds is shown in Scheme 12. The C−N coupling reaction catalyzed by a MOF‐74 probably takes place at the exposed copper location and follows a heterogeneous reaction mechanism.…”

Section: Coupling Reactions Catalyzed By Cu‐based Mofsmentioning

confidence: 99%

An Exploration on Copper‐Based Metal‐Organic Frameworks as Propitious Heterogeneous Catalyst for Coupling Reactions

et al. 2023

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Metal‐organic frameworks (MOFs) have been considered as adaptable alternatives of interest in catalytic reactions. Modern MOFs research and advancements strongly support their employment as catalysts to produce significant organic molecules. Concerning how such substances might be utilized in heterogeneous catalysis, the entire potency of MOFs in value‐added organic transformations must be thoroughly investigated. Standard MOFs components including encapsulation materials, linkers, metal‐nodes, and coated structures frequently provide effective catalytic active sites that provide ways to lessen human efforts to implement novel natural reactions. The significant aspects of using MOFs as recyclable catalysts are their convenient fabrication, consistent porosity, substantial pore volume, reusability and durable framework in addition to cost‐effectiveness. Since MOFs were extensively explored, they may have been used to fabricate medicinal active compounds through coupling and organic transformations. In this review, several Cu‐based MOFs are examined along with their catalytic attributes that assist with the selective fabrication of the product organic moieties via various cross‐coupling reactions.

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“…Anbardan et al addressed MOF composites and used Cu-MOF for the cross-coupling of amines and alcohols . They applied an oxidant to the catalyst, and the reaction was carried out in tetrahydrofuran (THF) solvent at room temperature for 24 h with a final yield of 10–86%.…”

Section: Introductionmentioning

confidence: 99%

Noble-Free Nanophotocatalyst of Ti_xFe_yLa_mO_z for Efficient Photocatalytic C–N Cross-Coupling Reactions under Visible Light

Dehghazi

Absalan

Gholizadeh

et al. 2023

ACS Appl. Nano Mater.

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Nanophotocatalysts are applied for different applications, and their usage has been enhanced remarkably since a decade. On the other hand, cross-coupling reactions of C−N bonds have found increasing popularity for coupling derivatives of organic compounds such as aniline using diverse catalysts. Nanoheterogeneous photocatalysts can offer suitable platforms for the C−N coupling of aniline derivatives. However, the design of a photocatalyst on the nanoscale with remarkable activity and selectivity, made of noble-free elements, is highly welcome. In this study, the half-filled electronic configuration and shallow trapping properties of Fe were employed to reduce the energy band gap of the system. Moreover, the large ionic radius of lanthanide leads to large surface activity. Thus, bi-and trinuclear nano-oxide nanophotocatalysts were synthesized based on the titanium, iron, and lanthanide elements (Ti x Fe y O z , Ti x Fe y La m O z ) to obtain logically designed photocatalysts with high selectivity, durability, and operation speed under visible light. In addition, designing photocatalysts in the nanoscale was the ultimate target of this study to use the highest benefit of the nanoscale, which is high surface activity. The developed nanophotocatalysts were used for coupling aniline and its 10 derivatives under visible light. The mechanism of the migration of electrons and the C−N reaction was also investigated in detail. In addition, both obtained nanophotocatalysts were applied in five different solvents and eight different conditions so the best condition for the reaction could be determined. Furthermore, the photocatalytic mechanism was studied in detail. The final nanocomposites were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), inductively coupled plasma mass spectrometry (ICP-MS), Brunauer−Emmett−Teller (BET) surface activity, Barrett−Joyner− Halenda (BJH) method, UV−vis spectroscopy, photoluminescence emission spectra, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), NMR spectra, mass spectra, and CHN elemental analysis. Both nanocomposites exhibited high photocatalytic activities in coupling aniline and its derivatives under visible light. However, the Ti x Fe y La m O z nanophotocatalyst showed a higher activity (90% conversion to obtain 2,4 dinitro-n-phenylaniline) than the Ti x Fe y O z nanophotocatalyst (68% conversion to obtain 2,4 dinitro-n-phenylaniline), which is mainly due to its higher surface activity because of its lanthanide content.

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Direct synthesis of amides and imines by dehydrogenative homo or cross-coupling of amines and alcohols catalyzed by Cu-MOF

Abstract: Oxidative dehydrogenative homo or cross-coupling of amines with alcohols to imines and amides was achieved with high to moderate yields at room temperature using Cu-MOF as an efficient and recyclable heterogeneous catalyst.

Cited by 18 publications

References 74 publications

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

An Exploration on Copper‐Based Metal‐Organic Frameworks as Propitious Heterogeneous Catalyst for Coupling Reactions

Noble-Free Nanophotocatalyst of Ti_xFe_yLa_mO_z for Efficient Photocatalytic C–N Cross-Coupling Reactions under Visible Light

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Direct synthesis of amides and imines by dehydrogenative homo or cross-coupling of amines and alcohols catalyzed by Cu-MOF

Abstract: Oxidative dehydrogenative homo or cross-coupling of amines with alcohols to imines and amides was achieved with high to moderate yields at room temperature using Cu-MOF as an efficient and recyclable heterogeneous catalyst.

Cited by 18 publications

References 74 publications

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N2O Atmosphere**

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N2O Atmosphere**

An Exploration on Copper‐Based Metal‐Organic Frameworks as Propitious Heterogeneous Catalyst for Coupling Reactions

Noble-Free Nanophotocatalyst of TixFeyLamOz for Efficient Photocatalytic C–N Cross-Coupling Reactions under Visible Light

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Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

Noble-Free Nanophotocatalyst of Ti_xFe_yLa_mO_z for Efficient Photocatalytic C–N Cross-Coupling Reactions under Visible Light