Prediction of the reactivity of 2(5H)-furanones as potential dienophiles in Diels–Alder reactions using philicity indexes

Benmeddah, Amel; Mekelleche, Sidi Mohamed; Benchouk, Wafaa; Mostefa‐Kara, Bachir; Villemin, Didier

doi:10.1016/j.theochem.2007.06.018

Cited by 10 publications

(6 citation statements)

References 41 publications

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“…The concepts of global and local electrophilicity parameters have been employed rigorously to interpret the reactivity patterns. , To have a better understanding of the impact of global electrophilicity parameters on DA mechanism, we have initialized our study with three dienes, namely, cyclopentadiene D-1 , furfural D-2 , dinitrofuran D-3 , and a series of dienophiles 1 − 10 (Scheme ). Optimized geometries of different dienes and dienophiles are depicted in Figures and , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…The results of these studies indicate a direct relationship between the decrease of cycloaddition activation barrier and charge transfer (CT) through a nonsynchronous bond-formation process . A great deal of work concerning the evaluation of global quantities based on DFT has been reported . Moreover, a significant amount of work exploring the local and global electrophilicity index to assign the regioselectivity of the DA interaction between unsymmetrical diene and dienophiles has also been documented successfully.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Evaluation of Global and Local Electrophilicity Patterns to Characterize Hetero-Diels−Alder Cycloaddition of Three-Membered 2H-Azirine Ring System

2009

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Present communication elicits an interesting interaction between 2H-azirine and a number of electron rich and electron deficient dienes. A series of substituted 2H-azirine 1-10, and three dienes namely cyclopentadiene D-1, furfural D-2, and dinitrofuran D-3 were chosen to investigate and critically review the reactivity and selectivity of Diels-Alder cycloaddition strategy. The global and local electrophilicity patterns have been evaluated to interpret the electrophilic/nucleophilic behavior of dienes D-1 to D-3 and dienophiles 1-10, in polar Diels-Alder cycloaddition, using the DFT method at the B3LYP/6-31G* level of theory. Regional nucleophilicity have been evaluated using local nucleophilicity descriptor N(k) (Perez, P.; Domingo, L. R.; Duque-Norena, M.; Chamorro, E. J. Mol. Struct. THEOCHEM 2009, 895, 86-91), and regional electrophilicity at the active sites of the interactive species involved in Diels-Alder processes have been described on a quantitative basis using local electrophilicity index omega(k).

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Evaluation of Global and Local Electrophilicity Patterns to Characterize Hetero-Diels−Alder Cycloaddition of Three-Membered 2H-Azirine Ring System

2009

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“…This reaction usually requires electron‐withdrawing groups in the dienophile and electron‐rich dienes, or vice versa , to afford acceptable reaction rates. The use of butenolides in DA reactions has been investigated over the last decades …”

Section: Introductionmentioning

confidence: 99%

Characterization of novel isobenzofuranones by DFT calculations and 2D NMR analysis

Teixeira

Alvarenga

2016

Magnetic Reson in Chemistry

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Phthalides are frequently found in naturally occurring substances and exhibit a broad spectrum of biological activities. In the search for compounds with insecticidal activity, phthalides have been used as versatile building blocks for the syntheses of novel potential agrochemicals. In our work, the Diels-Alder reaction between furan-2(5H)-one and cyclopentadiene was used successfully to obtain (3aR,4S,7R,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aS,4R,7S,7aR)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one (2) and (3aS,4S,7R,7aR)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aR,4R,7S,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one (3). The endo adduct (2) was brominated to afford (3aR,4R,5R,7R,7aS,8R)-5,8-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aS,4S,5S,7S,7aR,8S)-5,8-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one (4) and (3aS,4R,5R,6S,7S,7aR)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aR,4S,5S,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one (5). Following the initial analysis of the NMR spectra and the proposed two novel unforeseen products, we have decided to fully analyze the classical and non-classical assay structures with the aid of computational calculations. Computation to predict the (13) C and (1) H chemical shifts for mean absolute error analyses have been carried out by gauge-including atomic orbital method at M06-2X/6-31+G(d,p) and B3LYP/6-311+G(2d,p) levels of theory for all viable conformers. Characterization of the novel unforeseen compounds (4) and (5) were not possible by employing only the experimental NMR data; however, a more conclusive structural identification was performed by comparing the experimental and theoretical (1) H and (13) C chemical shifts by mean absolute error and DP4 probability analyses. Copyright © 2016 John Wiley & Sons, Ltd.

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“…The DA reaction is an essential tool for synthesis of complex molecules due to the formation of carbonecarbon bonds and construction of six-membered ring systems with stereoselective generation of four chiral centers in a single step [14]. The electron withdrawing nature of the ester carbonyl of a,bÀunsaturated g-lactones renders these substrates as excellent dienophiles in cycloaddition reactions with dienes [15,16].…”

Section: Introductionmentioning

confidence: 99%

Isolation and stereochemical assignment of phthalides resulting from the Diels–Alder reaction between 5-isopropoxyfuran-2(5H)-one and cyclopentadiene

Resende

Alvarenga

Willoughby

2015

Journal of Molecular Structure

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Prediction of the reactivity of 2(5H)-furanones as potential dienophiles in Diels–Alder reactions using philicity indexes

Cited by 10 publications

References 41 publications

Theoretical Evaluation of Global and Local Electrophilicity Patterns to Characterize Hetero-Diels−Alder Cycloaddition of Three-Membered 2H-Azirine Ring System

Theoretical Evaluation of Global and Local Electrophilicity Patterns to Characterize Hetero-Diels−Alder Cycloaddition of Three-Membered 2H-Azirine Ring System

Characterization of novel isobenzofuranones by DFT calculations and 2D NMR analysis

Isolation and stereochemical assignment of phthalides resulting from the Diels–Alder reaction between 5-isopropoxyfuran-2(5H)-one and cyclopentadiene

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