Stereo-, Regio-, and Chemoselective [3 + 2]-Cycloaddition of (2<i>E</i>,4<i>E</i>)-Ethyl 5-(Phenylsulfonyl)penta-2,4-dienoate with Various Azomethine Ylides, Nitrones, and Nitrile Oxides: Synthesis of Pyrrolidine, Isoxazolidine, and Isoxazoline Derivatives and a Computational Study

Sankar, Ulaganathan; Kumar, Ch. Venkata Surya; Subramanian, V.; Balasubramanian, K. K.; Mahalakshimi, S.

doi:10.1021/acs.joc.5b02845

Cited by 16 publications

(9 citation statements)

References 64 publications

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“…The reaction mechanisms of the 32CA reactions of NOs with ethylene and acetylene derivatives, as well as the study of the regioselectivity in the formation of the two isoxazolines, have been widely analysed within the Density Functional Theory (DFT) framework . Fulminic acid 2 , the simplest NO, presents a high activation enthalpy toward ethylene 10 , 13.3 kcal·mol −1 , and toward acetylene 11 , 13.7 kcal·mol −1 …”

Section: Introductionmentioning

confidence: 99%

Understanding the reactivity and regioselectivity of [3 + 2] cycloaddition reactions between substituted nitrile oxides and methyl acrylate. A molecular electron density theory study

Ndassa

Adjieufack

Ketcha

et al. 2017

Int J of Quantum Chemistry

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The [3 + 2] cycloaddition (32CA) reactions of three nitrile oxides (NOs) (R‐CNO; R = Ph, CO2Me, and Br) with methyl acrylate (MA) have been theoretically studied within the molecular electron density theory. Topological analysis of the electron localization function of these NOs permits to establish that they will participate in zw‐type 32CA reactions. Analysis of the conceptual DFT indices indicates that these zw‐type 32CA reactions will have a low polar character as a consequence of the relatively low electrophilic character of MA and the low nucleophilic character of NOs, in agreement with the global electron density transfer computed at the corresponding TSs. The activation enthalpies associated with these 32CA reactions range from 8.2 to 12.7 kcal·mol−1. The presence of the bromide atom provokes the larger acceleration. While the 32CA reaction involving the CO2Me substituted NO is highly ortho regioselective, the other two reactions are poorly ortho regioselective. A bonding evolution theory study of the more favorable ortho regiosiomeric channel associated with the 32CA reaction involving the Br substituted NO indicates that this reaction is associated to a nonconcerted two‐stage one‐step mechanism, in which the activation energy is mainly related to the initial rupture of the CN triple bond of the NO.

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Section: Introductionmentioning

confidence: 99%

Understanding the reactivity and regioselectivity of [3 + 2] cycloaddition reactions between substituted nitrile oxides and methyl acrylate. A molecular electron density theory study

Ndassa

Adjieufack

Ketcha

et al. 2017

Int J of Quantum Chemistry

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“…Subramanian et al 27 have shown that the chemoselectivity of the cycloaddition of azomethine ylides to (2E,4E)ethyl 5-(phenylsulfonyl)penta-2,4-dienoate (65) for the synthesis of spiropyrrolidines 66 (24-78% yields) was dependent upon the nature of the dipole as well as its steric bulk (Scheme 21). In the case of nitrile oxides, the cycloaddition occurred at the acrylate double bond.…”

Section: Scheme 20 13-dipolar Cycloaddition Reaction Of Curcumin (63mentioning

confidence: 99%

Recent Advances in the Synthesis of Hetero- and Carbocyclic Compounds and Complexes Based on Acenaphthylene-1,2-dione

Yavari

Khajeh-Khezri²

2018

Synthesis

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Acenaphthylene-1,2-dione has been utilized in a wide range of reactions as a starting material for the synthesis of hetero- and carbocyclic compounds and complexes. This review provides a short summary of the recent advances in the application of acenaphthylene-1,2-dione in the synthesis of hetero- and carbocyclic systems and bioactive compounds. In addition, the applications of acenaphthylene-1,2-dione in the synthesis of spiro compounds, propellanes, and ligands in catalyst reactions, from 2002 to early 2018, are included.1 Introduction2 Synthesis of Spiro Compounds Employing Acenaphthylene-1,2-dione2.1 Methods for the Construction of Spiro Compounds2.1.1 By 1,3-Dipolar Cycloaddition of Acenaphthylene-1,2-dione via Azomethine Ylides2.1.2 By Multicomponent Reactions of Acenaphthylene-1,2-dione with C–H Acidic Compounds2.1.3 By Reaction of Acenaphthylene-1,2-dione with Zwitterionic Intermediates2.1.4 By Substitution and Multicomponent Reactions of Acenaphth- ylene-1,2-dione with Different Nucleophiles3 Synthesis of Propellanes by Employing Acenaphthylene-1,2-dione3.1 Methods for the Construction of Propellanes Based on Acenaph- thylene-1,2-dione3.1.1 By Reaction of Acenaphthylene-1,2-dione with Nucleophiles3.1.2 By Reaction of Acenaphthylene-1,2-dione with Binucleophiles4 Synthesis of Ligands Employing Acenaphthylene-1,2-dione for Catalyst Reactions5 Synthesis of Novel Hetero- and Carbocyclic Compounds Employing Acenaphthylene-1,2-dione5.1 By Reaction of Acenaphthylene-1,2-dione with Nucleophiles5.2 By Reaction of Acenaphthylene-1,2-dione with Zwitterionic Intermediates5.3 By Ring Opening and Ring Enlargement6 Conclusion

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“…1,3-Dipolar cycloaddition (1,3-DC) of stabilized azomethine ylides based on ninhydrin and α-amino acids to activated alkenes or alkynes represents a concise and the most convenient method for the regio- and stereoselective synthesis of spiropyrroli(zi)dine and spiropyrroli(zi)ne ring systems . Usually, ninhydrin-derived ylides are generated in situ and used in the reaction without isolation.…”

Section: Introductionmentioning

confidence: 99%

Catalyst-free Tandem 1,3-Dipolar Cycloaddition/Aldol Condensation: Diastereoselective Construction of the Azatetraquinane Skeleton

et al. 2020

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The one-pot regioselective and diastereoselective method for the synthesis of 5-(het)aroyl-7-(het)arylhexahydrobenzo[4,5]pentaleno[1,6a-b](thia)pyrrolizine-6,12-diones from accessible 1,5-di(het)arylpent-4-ene-1,3-diones or curcuminoids in 38–98% yield was developed. This reaction proceeds as a sequence of 1,3-dipolar cycloaddition of azomethine ylide generated in situ from ninhydrin and (thia)proline at the CC bond of corresponding enedione, followed by spontaneous intramolecular aldol condensation and leads to the formation of an azatetraquinane scaffold.

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Stereo-, Regio-, and Chemoselective [3 + 2]-Cycloaddition of (2E,4E)-Ethyl 5-(Phenylsulfonyl)penta-2,4-dienoate with Various Azomethine Ylides, Nitrones, and Nitrile Oxides: Synthesis of Pyrrolidine, Isoxazolidine, and Isoxazoline Derivatives and a Computational Study

Cited by 16 publications

References 64 publications

Understanding the reactivity and regioselectivity of [3 + 2] cycloaddition reactions between substituted nitrile oxides and methyl acrylate. A molecular electron density theory study

Understanding the reactivity and regioselectivity of [3 + 2] cycloaddition reactions between substituted nitrile oxides and methyl acrylate. A molecular electron density theory study

Recent Advances in the Synthesis of Hetero- and Carbocyclic Compounds and Complexes Based on Acenaphthylene-1,2-dione

Catalyst-free Tandem 1,3-Dipolar Cycloaddition/Aldol Condensation: Diastereoselective Construction of the Azatetraquinane Skeleton

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Stereo-, Regio-, and Chemoselective [3 + 2]-Cycloaddition of (2E,4E)-Ethyl 5-(Phenylsulfonyl)penta-2,4-dienoate with Various Azomethine Ylides, Nitrones, and Nitrile Oxides: Synthesis of Pyrrolidine, Isoxazolidine, and Isoxazoline Derivatives and a Computational Study

Cited by 16 publications

References 64 publications

Understanding the reactivity and regioselectivity of [3 + 2] cycloaddition reactions between substituted nitrile oxides and methyl acrylate. A molecular electron density theory study

Understanding the reactivity and regioselectivity of [3 + 2] cycloaddition reactions between substituted nitrile oxides and methyl acrylate. A molecular electron density theory study

Recent Advances in the Synthesis of Hetero- and Carbocyclic Compounds­ and Complexes Based on Acenaphthylene-1,2-dione

Catalyst-free Tandem 1,3-Dipolar Cycloaddition/Aldol Condensation: Diastereoselective Construction of the Azatetraquinane Skeleton

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Recent Advances in the Synthesis of Hetero- and Carbocyclic Compounds and Complexes Based on Acenaphthylene-1,2-dione