Peroxidation of 2-oxindole and barbituric acid derivatives under batch and continuous flow using an eco-friendly ethyl acetate solvent

Chaudhari, Moreshwar B.; Mohanta, Nirmala; Pandey, Akanksha M.; Vandana, Madhusoodhanan; Karmodiya, Krishanpal; Gnanaprakasam, Boopathy

doi:10.1039/c9re00068b

Cited by 15 publications

(11 citation statements)

References 41 publications

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“…Organic peroxides offer a largely uncharted chemical space for the development of new medicinal agents with antimalarial, − anthelmintic, − anticancer, − fungicidal, , antitubercular, − and antiviral − activities. Artemisinin, a natural peroxide recognized by the 2015 Nobel Prize in Medicine to Youyou Tu, and its synthetic analogues such as arterolane are important antimalarial drugs.…”

Section: Introductionmentioning

confidence: 99%

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

et al. 2021

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Stable bridged azaozonides can be selectively assembled via a catalyst-free three-component condensation of 1,5-diketones, hydrogen peroxide, and an NH-group source such as aqueous ammonia or ammonium salts. This procedure is scalable and can produce gram quantities of bicyclic stereochemically rich heterocycles. The new azaozonides are thermally stable and can be stored at room temperature for several months without decomposition and for at least 1 year at −10 °C. The chemical stability of azaozonides was explored for their subsequent selective transformations including the first example of an aminoperoxide rearrangement that preserves the peroxide group. The amino group in aminoperoxides has remarkably low nucleophilicity and does not participate in the usual amine alkylation and acylation reactions. These observations and the 15 pK a units decrease in basicity in comparison with a typical dialkyl amine are attributed to the strong hyperconjugative nN→σ*C–O interaction with the two antiperiplanar C–O bonds. Due to the weakness of the complementary nO→σ*C–N donation from the peroxide oxygens (a consequence of “inverse α-effect”), this interaction depletes electron density from the NH moiety, protects it from oxidation, and makes it similar in properties to an amide.

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Section: Introductionmentioning

confidence: 99%

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

et al. 2021

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“…It should be noted that the nucleophilic attack can proceed via the S N 1 pathway. On the contrary, in the case of the azidation of peroxyoxindoles, at first Amberlyst-15 leads to the deprotection of 4 to give A . In the next step, the distant oxygen atom of A coordinates to TMS because of the high affinity of oxygen for silicon, thereby making N 3 – free nucleophile.…”

Section: Resultsmentioning

confidence: 99%

Continuous-Flow Direct Azidation of Alcohols and Peroxides for the Synthesis of Quinoxalinone, Benzooxazinone, and Triazole Derivatives

2022

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Continuous-flow reactors provide an ideal tool for the synthesis of potentially explosive but synthetically useful organic substances like organic azides due to their intrinsically small volume leading to very effective collision and highly controlled reaction conditions. Herein, we report the continuous-flow direct azidation of various alcohols by using TMSN 3 as an azide transfer reagent in the presence of Amberlyst-15 as a recyclable catalyst. Numerous 3hydroxy-2-oxindoles effectively undergo azide transfer to afford azidefunctionalized quaternary stereocenters in a continuous-flow module. Interestingly, peroxyoxindole undergoes sequential skeletal rearrangement to generate a carbocation followed by nucleophilic azidation to afford a library of substituted 2-azido-2H-benzo[b][1,4]oxazin-3(4H)-one derivatives under continuous flow. Furthermore, a continuous-flow Cu-catalyzed click reaction afforded triazole-functionalized deivatives. Next, reduction of azide in the presence of PPh 3 affords the amine derivatives in good yields. The continuous-flow application was extended further for the thermolytic skeletal rearrangement of 3-azide-2-oxindole for the synthesis of biologically important quinoxalin-2(1H)-ones without any reagents. Furthermore, this continuous-flow direct azidation reaction is scaled up to 6.144 g of azides with a turnover number of 9.24 under safer conditions.

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“…The graphical solution of Equation (10) in semilog coordinates (ln ½1 − m t /m ∞t) (Figure 7) allows us to calculate D 2 :…”

Section: Oz Release From Mps and Fsmentioning

confidence: 99%

“…The discovery of the natural peroxide artemisinin [1][2][3], which has antimalarial properties, was the beginning of the development of biologically active peroxides (Figure 1). It has been found that cyclic peroxides have antimalarial [4][5][6][7][8][9][10][11][12], antiparasitic [13][14][15][16][17][18][19], anticancer [20][21][22][23][24][25][26][27][28][29][30][31], antiviral [32][33][34], and fungicidal [18,35,36] activities. On the basis of the fully synthetic peroxide arterolane, which contains a 1,2,4-trioxolane (ozonide) fragment, has been created an antimalarial drug of the latest generation-Synriam [37].…”

Section: Introductionmentioning

confidence: 99%

Development of Biodegradable Delivery Systems Containing Novel 1,2,4-Trioxolane Based on Bacterial Polyhydroxyalkanoates

Lipaikin

Yaremenko

Terent’ev

et al. 2022

Advances in Polymer Technology

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In this work, delivery systems in the form of microparticles and films containing 1,2,4-trioxolane (ozonide, OZ) based on polyhydroxyalkanoates (PHAs) were developed. Main systems’ characteristics were investigated: the particle yield, average diameter, zeta potential, surface morphology, loading capacity, and drug release profile of microparticles, as well as surface morphology and release profiles of OZ-containing films. PHA-based OZ-loaded microparticles have been found to have satisfactory size, zeta potential, and ozonide loading-release behavior. It was noted that OZ content influenced the surface morphology of obtained systems.

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Peroxidation of 2-oxindole and barbituric acid derivatives under batch and continuous flow using an eco-friendly ethyl acetate solvent

Abstract: We have demonstrated the magnetically retrievable Fe(OH)3Fe3O4catalyzed C–H peroxidation of 2-oxindole and barbituric acid derivatives under batch and continuous flow process for the first time.

Cited by 15 publications

References 41 publications

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

Continuous-Flow Direct Azidation of Alcohols and Peroxides for the Synthesis of Quinoxalinone, Benzooxazinone, and Triazole Derivatives

Development of Biodegradable Delivery Systems Containing Novel 1,2,4-Trioxolane Based on Bacterial Polyhydroxyalkanoates

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