Recent progress in the field of cycloaddition reactions involving conjugated nitroalkenes

Łapczuk-Krygier, Agnieszka; Kącka‐Zych, Agnieszka; Kula, Karolina

doi:10.5267/j.ccl.2018.12.002

Cited by 26 publications

(19 citation statements)

References 43 publications

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“…The most universal methodology for preparing nitrofunctionalized cyclic compounds is cycloaddition reactions involving respective conjugated nitroalkenes (CNA) [4,11]. In this way, several four- [12,13], five - [14][15][16][17], and six-membered [18][19][20][21] nitro-cycles have been prepared.…”

Section: Introductionmentioning

confidence: 99%

“…All these processes have been realized under relatively mild conditions and with full atomic economy. A detailed literature survey shows, unfortunately, [11], that any examples of [2 + 1]-cycloaddition involving conjugated nitroalkenes (which gave the possibility of the synthesis of nitro-functionalized cyclopropanes) are not known. The work presented here initiates a comprehensive study in this area.…”

Section: Introductionmentioning

confidence: 99%

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Competition between [2 + 1]- and [4 + 1]-cycloaddition mechanisms in reactions of conjugated nitroalkenes with dichlorocarbene in the light of a DFT computational study

Alnajjar

Jasiński

2019

J Mol Model

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The competition between [2 + 1] and [4 + 1] channels regarding reactions of conjugated nitroalkenes with dichlorocarbene was explored based on B3LYP/6-31G(d) calculations. It was found that, in the case of cycloadditions involving parent nitroethene and its 1-substituted analogs, the [2 + 1] scheme should be treated as possible only from the kinetic process point of view. On the other hand, in similar reactions involving 2-substituted nitroethenes, both channels considered may compete. Additionally, mechanistic aspects of all cycloadditions were analyzed. It was found that the considered [2 + 1]-cycloadditions proceed via a non-polar mechanism with a biradicaloidal transition state (TS), whereas [4 + 1]-cycloadditions proceed via a polar mechanism with a zwitterionic TS.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Competition between [2 + 1]- and [4 + 1]-cycloaddition mechanisms in reactions of conjugated nitroalkenes with dichlorocarbene in the light of a DFT computational study

Alnajjar

Jasiński

2019

J Mol Model

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“…The [3+2] cycloadditions (32CA) are all-purpose strategiesto the regio-and stereoselective synthesis of five-membered heterocyclic molecular systems [1][2][3][4]. These types of reactions generally proceed under mild conditions, without the presence of catalysts, giving high yields of target compounds [2][3][4]. Furthermore, 32CA are realized with "full atomic economy."…”

Section: Introductionmentioning

confidence: 99%

“…It is particularly important for the green chemistry aspect [5]. Due to the listed advantages, 32CA are increasingly used by experimental chemists, mainly because of the possibility for using heterocyclic compounds in pharmacology [3,6,7]. The application of 32CA for synthesis has also increased interest among researchers in the theoretical sciences.…”

Section: Introductionmentioning

confidence: 99%

Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study

Zawadzińska

Kula

2021

Organics

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The regiochemistry of [3+2] cycloaddition (32CA) processes between benzonitrile N-oxide 1 and β-phosphorylated analogues of nitroethenes 2a–c has been studied using the Density Functional Theory (DFT) at the M062X/6-31+G(d) theory level. The obtained results of reactivity indices show that benzonitrile N-oxide 1 can be classified both as a moderate electrophile and moderate nucleophile, while β-phosphorylated analogues of nitroethenes 2a–c can be classified as strong electrophiles and marginal nucleophiles. Moreover, the analysis of CDFT shows that for [3+2] cycloadditions with the participation of β-phosphorylatednitroethene 2a and β-phosphorylated α-cyanonitroethene 2b, the more favored reaction path forms 4-nitro-substituted Δ2-isoxazolines 3a–b, while for a reaction with β-phosphorylated β-cyanonitroethene 2c, the more favored path forms 5-nitro-substituted Δ2-isoxazoline 4c. This is due to the presence of a cyano group in the alkene. The CDFT study correlates well with the analysis of the kinetic description of the considered reaction channels. Moreover, DFT calculations have proven the clearly polar nature of all analyzed [3+2] cycloaddition reactions according to the polar one-step mechanism.

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“…This cannot be primary reaction product because it is widely known that cycloaddition processes proceed with full atomic economy [ 7 , 8 ]. So, we assumed, that primary product is 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline 3 , which spontaneously decomposed, partially with HCl extrusion.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

et al. 2021

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The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.

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Recent progress in the field of cycloaddition reactions involving conjugated nitroalkenes

Abstract: In this review we present recent progress in the cycloaddition reactions of conjugated nitroalkenes with alkenes, conjugated 1,3-dienes or three atoms components (eg. nitrones, azides, diazocompounds, azomethine imines and ylides).

Cited by 26 publications

References 43 publications

Competition between [2 + 1]- and [4 + 1]-cycloaddition mechanisms in reactions of conjugated nitroalkenes with dichlorocarbene in the light of a DFT computational study

Competition between [2 + 1]- and [4 + 1]-cycloaddition mechanisms in reactions of conjugated nitroalkenes with dichlorocarbene in the light of a DFT computational study

Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

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