Oxazole as an Electron-Deficient Diene in the Diels–Alder Reaction

Suárez-Moreno, Galdina V.; González‐Zamora, Eduardo; Méndez, Francisco

doi:10.1021/ol202648r

Cited by 17 publications

(7 citation statements)

References 31 publications

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“…The negative values of the free energy for the dehydrogenation reactions of the adducts favor the growth of the fragments. Motivated by these results and others [ 35 , 36 ], experimental studies of the reactivity of the current systems are underway.…”

Section: Discussionmentioning

confidence: 94%

Growth of Fullerene Fragments Using the Diels-Alder Cycloaddition Reaction: First Step towards a C60 Synthesis by Dimerization

Mojica

Méndez²,

Alonso³

2013

Molecules

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Density Functional Theory has been used to model the Diels-Alder reactions of the fullerene fragments triindenetriphenilene and pentacyclopentacorannulene with ethylene and 1,3-butadiene. The purpose is to prove the feasibility of using Diels-Alder cycloaddition reactions to grow fullerene fragments step by step, and to dimerize fullerene fragments, as a way to obtain C60. The dienophile character of the fullerene fragments is dominant, and the reaction of butadiene with pentacyclopentacorannulene is favored.

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Section: Discussionmentioning

confidence: 94%

Growth of Fullerene Fragments Using the Diels-Alder Cycloaddition Reaction: First Step towards a C60 Synthesis by Dimerization

Mojica

Méndez²,

Alonso³

2013

Molecules

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“…The geometries of substituted triindenetriphenylene 1 and pentacyclopentacorannulene 2 depicted in Figure 2 have been fully optimized at the B3LYP level of theory, with the 6-31G(d,p) basis set to expand the electronic wave functions. The B3LYP exchange-correlation functional has been used to study the pi-sigma conversion in C-C bond formation in the Diels-Alder cycloaddition reaction of oxazole with ethylene [25], and the sp 2 -sp conversion for carbenes [26]. Also the addition of polarization functions improves the description of the pi-sigma conversion in the C-C bond formation [27].…”

Section: Methodsmentioning

confidence: 99%

The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents

2016

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Abstract:The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH2, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF3, CHO, CN, NO2). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO2 substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

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“…57 The dehydration of cationic Diels-Alder cycloadducts was also found to be a highly exothermic process, favoring formation of pyridinium cations. Therefore, the best strategy to harness the potential of oxazole as a diene in IEDDA reaction is to use a proton-assisted process (i.e., to exploit the electron-poor oxazolium cation).…”

Section: %mentioning

confidence: 99%