Hemin-catalyzed controlled oxidative cyanation of secondary amine for the synthesis of α-aminonitriles and α-iminonitriles

Li, Fengxi; Xu, Yaning; Xu, Yuelin; Wang, Qianqian; Ma, Jinglin; Chen, Peng; Wang, Lei

doi:10.1016/j.mcat.2022.112576

Cited by 5 publications

(5 citation statements)

References 41 publications

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“…The starting aminofuranes were easily prepared by reduction of Schiff bases (formed by condensation of the corresponding mono- or bis-amines with furfural) with sodium borohydride in methanol [ 83 , 108 – 111 ]. In order to determine the optimum reaction conditions, a series of reactions between N -benzyl-1-(furan-2-yl)methanamine ( 1a ) and maleic anhydride were carried out and the results obtained are shown in Table 1 .…”

Section: Resultsmentioning

confidence: 99%

Sustainable tandem acylation/Diels–Alder reaction toward versatile tricyclic epoxyisoindole-7-carboxylic acids in renewable green solvents

Yıldırım

2024

Beilstein J. Org. Chem.

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Tandem Diels–Alder reactions are often used for the straightforward formation of complex natural compounds and the fused polycyclic systems contained in their precursors. In the second step of this reaction, regio- and stereochemically controlled intramolecular cyclization leads to the formation of versatile nitrogen-containing tricyclic systems. However, these useful organic transformations are usually carried out in highly toxic organic solvents such as benzene, toluene, chloroform, etc. Despite recent efforts by 'green chemists', synthetic chemists still use these traditional toxic organic solvents in many of their reactions, even though safer alternatives are available. However, in addition to the harmful effects of these petrochemical solvents on the environment, the prediction that their resources will run out in the near future has led 'green chemists' to explore solvents that can be derived from renewable resources and used effectively in various organic transformations. In this context, we have shown for the first time that the 100% atom-economical tandem Diels–Alder reaction between aminofuranes and maleic anhydride can be carried out successfully in vegetable oils and waxes. The reaction was successfully carried out in sunflower seed oil, olive oil, oleic acid and lauryl myristate under mild reaction conditions. A series of epoxyisoindole-7-carboxylic acid and bisepoxyisoindole-7-carboxylic acids were obtained in good yields after a practical isolation procedure. The results obtained in this study demonstrate the potential of vegetable oils and their renewable materials to provide a reaction medium that is more sustainable than conventional organic solvents in cascade Diels–Alder reactions and can be used repeatedly without significant degradation. These materials also allow the reaction to be completed in less time, with less energy consumption and higher yields.

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Section: Resultsmentioning

confidence: 99%

Sustainable tandem acylation/Diels–Alder reaction toward versatile tricyclic epoxyisoindole-7-carboxylic acids in renewable green solvents

Yıldırım

2024

Beilstein J. Org. Chem.

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“…As reported in this work, hemin concentrations as low as 2 nM can be detected, although we did not investigate the limit of detection. With some modifications, the system described could probably also be applied for the detection and determination of glucose. , Finally, synthetic applications of the hemin-SDS- l -His system could also be possible for all those cases where hemin was shown previously to act as a catalyst, for example, for the transformation of nitrosamines (water pollutants), the oxidative cyanation of secondary amines, and sulfonium ylide formation . Interestingly, hemin-catalyzed reactions can also occur under aerobic conditions in the absence of a peroxide. − It remains to be investigated whether the system reported in this work could be applied to those reactions or similar reactions.…”

Section: Discussionmentioning

confidence: 99%

“…With some modifications, the system described could probably also be applied for the detection and determination of glucose. 175,176 Finally, synthetic applications of the hemin-SDS-L-His system could also be possible for all those cases where hemin was shown previously to act as a catalyst, for example, for the transformation of nitrosamines 177 (water pollutants), the oxidative cyanation of secondary amines, 178 and sulfonium ylide formation. 179 Interestingly, hemin-catalyzed reactions can also occur under aerobic conditions in the absence of a peroxide.…”

Section: The Activity Of Hemin At [Sds]mentioning

confidence: 99%

Optimization and Enhancement of the Peroxidase-like Activity of Hemin in Aqueous Solutions of Sodium Dodecylsulfate

Cvjetan,

Schuler,

Ishikawa

et al. 2023

ACS Omega

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Iron porphyrins play several important roles in present-day living systems and probably already existed in very early life forms. Hemin (= ferric protoporphyrin IX = ferric heme b), for example, is the prosthetic group at the active site of heme peroxidases, catalyzing the oxidation of a number of different types of reducing substrates after hemin is first oxidized by hydrogen peroxide as the oxidizing substrate of the enzyme. The active site of heme peroxidases consists of a hydrophobic pocket in which hemin is embedded noncovalently and kept in place through coordination of the iron atom to a proximal histidine side chain of the protein. It is this partially hydrophobic local environment of the enzyme which determines the efficiency with which the sequential reactions of the oxidizing and reducing substrates proceed at the active site. Free hemin, which has been separated from the protein moiety of heme peroxidases, is known to aggregate in an aqueous solution and exhibits low catalytic activity. Based on previous reports on the use of surfactant micelles to solubilize free hemin in a nonaggregated state, the peroxidase-like activity of hemin in the presence of sodium dodecyl sulfate (SDS) at concentrations below and above the critical concentration for SDS micelle formation (critical micellization concentration (cmc)) was systematically investigated. In most experiments, 3,3′,5,5′-tetramethylbenzidine (TMB) was applied as a reducing substrate at pH = 7.2. The presence of SDS clearly had a positive effect on the reaction in terms of initial reaction rate and reaction yield, even at concentrations below the cmc. The highest activity correlated with the cmc value, as demonstrated for reactions at three different HEPES concentrations. The 4-(2-hydroxyethyl)-1-piperazineethanesulfonate salt (HEPES) served as a pH buffer substance and also had an accelerating effect on the reaction. At the cmc, the addition of l-histidine (l-His) resulted in a further concentration-dependent increase in the peroxidase-like activity of hemin until a maximal effect was reached at an optimal l-His concentration, probably corresponding to an ideal mono-l-His ligation to hemin. Some of the results obtained can be understood on the basis of molecular dynamics simulations, which indicated the existence of intermolecular interactions between hemin and HEPES and between hemin and SDS. Preliminary experiments with SDS/dodecanol vesicles at pH = 7.2 showed that in the presence of the vesicles, hemin exhibited similar peroxidase-like activity as in the case of SDS micelles. This supports the hypothesis that micelle- or vesicle-associated ferric or ferrous iron porphyrins may have played a role as primitive catalysts in membranous prebiotic compartment systems before cellular life emerged.

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“…1–10 Over the past decades, the scope of enzymatic applications in non-natural reactions has significantly expanded, thereby broadening their utility in chemical synthesis. 11–31 Hemoproteins, including cytochrome, peroxidase, myoglobin, and hemoglobin, have demonstrated the ability to mediate carbene-type C–C bond formations such as cyclopropanation, C–H insertion and ylide formation. 32–39 These remarkable achievements have unveiled an entirely new and unexpected realm of organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Vitreoscillahemoglobin: a natural carbene transfer catalyst for diastereo- and enantioselective synthesis of nitrile-substituted cyclopropanes

Wang

et al. 2023

Green Chem.

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Hemin-catalyzed controlled oxidative cyanation of secondary amine for the synthesis of α-aminonitriles and α-iminonitriles

Cited by 5 publications

References 41 publications

Sustainable tandem acylation/Diels–Alder reaction toward versatile tricyclic epoxyisoindole-7-carboxylic acids in renewable green solvents

Sustainable tandem acylation/Diels–Alder reaction toward versatile tricyclic epoxyisoindole-7-carboxylic acids in renewable green solvents

Optimization and Enhancement of the Peroxidase-like Activity of Hemin in Aqueous Solutions of Sodium Dodecylsulfate

Vitreoscillahemoglobin: a natural carbene transfer catalyst for diastereo- and enantioselective synthesis of nitrile-substituted cyclopropanes

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