Arylnitroalkenes as scavengers of macrophage-generated oxidants

The reaction of cyclic nitronic esters (isoxazoline- and 5,6-dihydro-4H-1,2-oxazine-N-oxides) with hydrochloric acid affords geminal chloronitroso compounds bearing a distant hydroxyl group. The reaction is usually diastereoselective, and in some cases stereodivergent formation of isomers at different temperatures is observed. The discovered process represents the first example of an interrupted Nef reaction of nitronic esters. DFT calculations support the initial formation of N,N-bis(oxy)iminium cations (key intermediates in the Nef reaction), which are intercepted by the chloride anion followed by ring opening. The synthetic utility of the resulting functionalized chloronitroso compounds in the Diels–Alder reaction with cyclopentadiene was demonstrated.

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“…Prepared according to the general procedure from ( E )-1-chloro-4-(2-nitroprop-1-en-1-yl)benzene (192 mg, 0.97 mmol). Yield: 146 mg (59%).…”

Section: Methodsmentioning

confidence: 99%

“…rel-(4S,4aR,7aR)-4-(4-Chlorophenyl)- 3-methyl-4,4a,5,6,7,7ahexahydrocyclopenta[e] [1,2]oxazine 2-Oxide (2c). Prepared according to the general procedure from (E)-1-chloro-4-(2-nitroprop-1-en-1-yl)benzene 43 (198 mg, 1.0 mmol). Yield: 207 mg (78%).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds

et al. 2022

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“…Nitroalkenes are versatile building blocks 7 because they have been widely used as substrates such as Michael addition, 1,8 Friedel-Cras alkylation, 9,10 1,3-dipolar cycloaddition 11,12 and domino reaction. 13 They have also been used as key precursors of different targets for scavengers of macrophage-generated oxidants, 14 antidepressant drugs 15 and rat even human monoamine oxidase inhibitors. 16 The nitro group can be converted into various functional groups.…”

Section: Introductionmentioning

confidence: 99%

Ethylenediamine-functionalized magnetic Fe₃O₄@SiO₂ nanoparticles: cooperative trifunctional catalysis for selective synthesis of nitroalkenes

Xue

Dong

et al. 2015

RSC Adv.

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A magnetically separable trifunctional nanocatalyst Fe 3 O 4 @SiO 2 -NH 2 was synthesized and characterized by TEM, FT-IR, XRD, TGA, and EA. The designed nanocatalyst was found to be highly active for selective synthesis of nitroalkenes with nitromethane and aromatic aldehyde through cooperative trifunctional catalysis of primary amine, secondary amine and Si-OH groups on the surface of catalyst. Under the optimized conditions, various representative substrates were extended to obtain the corresponding products in a moderate or excellent yield. After reaction, the trifunctional nanocatalyst was easily recovered and recycled by applying an external magnet. In addition, a possible cooperative trifunctional catalysis mechanism was also proposed.

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Asymmetric Conjugate Addition of 3‐Hydroxychromen‐4‐Ones to Electron‐Deficient Olefins Catalyzed by Recyclable C₂‐Symmetric Squaramide

et al. 2021

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The readily scalable asymmetric synthesis of the chiral chromone derivatives functionalized at position 2 via electrophilic enantioselective olefination of the chromone core with nitroolefins and ß,γ‐unsaturated α‐ketoesters in the presence of simple C2‐symmetric tertiary amine‐squaramide catalyst was developed. The reaction products were obtained in 80–99% yield with 89–99% ee in 95% EtOH. The absolute configurations of the synthesized chromone derivatives were unambiguously established by transformation of compound (R)‐3 aa to known methyl (R)‐β‐nitro‐α‐phenylpropionate and by the single crystal XRD analysis of compounds (R,S)‐5 aa and (R,S)‐5 ab. Catalyst V poorly soluble in common organic solvents could be easily separated from the reaction mixture and reused up to 10 catalytic cycles. Catalytic hydrogenation and esterification reactions of the synthesized compounds were carried out to demonstrate synthetic potential of the developed procedure.

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Arylnitroalkenes as scavengers of macrophage-generated oxidants

Cited by 8 publications

References 44 publications

Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds

Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds

Ethylenediamine-functionalized magnetic Fe₃O₄@SiO₂ nanoparticles: cooperative trifunctional catalysis for selective synthesis of nitroalkenes

Asymmetric Conjugate Addition of 3‐Hydroxychromen‐4‐Ones to Electron‐Deficient Olefins Catalyzed by Recyclable C₂‐Symmetric Squaramide

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Arylnitroalkenes as scavengers of macrophage-generated oxidants

Cited by 8 publications

References 44 publications

Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds

Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds

Ethylenediamine-functionalized magnetic Fe3O4@SiO2 nanoparticles: cooperative trifunctional catalysis for selective synthesis of nitroalkenes

Asymmetric Conjugate Addition of 3‐Hydroxychromen‐4‐Ones to Electron‐Deficient Olefins Catalyzed by Recyclable C2‐Symmetric Squaramide

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Product

Resources

About

Ethylenediamine-functionalized magnetic Fe₃O₄@SiO₂ nanoparticles: cooperative trifunctional catalysis for selective synthesis of nitroalkenes

Asymmetric Conjugate Addition of 3‐Hydroxychromen‐4‐Ones to Electron‐Deficient Olefins Catalyzed by Recyclable C₂‐Symmetric Squaramide