Diels–Alder reactions for the rational design of benzo[b]thiophenes: DFT-based guidelines for synthetic chemists

Brasca, Romina; Kneeteman, Marı́a N.; Mancini, Paolo; Fabian, Walter M. F.

doi:10.1016/j.molstruc.2011.11.050

Cited by 3 publications

(1 citation statement)

References 129 publications

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“…2 In continuation of our previous computational studies concerning Diels-Alder reactions of nitro-substituted furans and thiophenes here we want to present the results of the analogous reaction of 2-nitro-1-tosylpyrrole 2c with Danischefsky's diene 5. [3][4][5] Experimentally, the sole product found in this reaction is 5-hydroxy-1-tosylindole (Scheme 1).…”

Section: Introductionmentioning

confidence: 94%

Reactivity, Stereo- And Regioselectivity of Diels-Alder Reactions Between Five-Membered Heterocycles and Danishefsky's Diene

Brasca

Kneeteman

Mancini

et al. 2013

Proceedings of the 17th International Electronic Conference on Synthetic Organic Chemistry

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Conceptual density functional theory (chemical hardness η, electronic chemical potential µ, global and local electrophilicity index ω and ω k , Fukui function f + k) is used to predict reactivity, stereo-and regioselectivity of the Diels-Alder (DA) reaction between 2-nitropyrrole and its 1tosylated derivative with Danishefsky's diene to yield 5-hydroxyindoles. A detailed mechanistic study of various possible reaction channels is done by DFT [B3LYP/6-31G(d)] calculations. Solvent effects (benzene) are taken into account by the CPCM bulk solvation model. In principle, the nitropyrrole can either act as diene involving the nitro group (hetero Diels-Alder reaction, HAD) or alternatively as alkene in a "normal" Diels-Alder reaction. The experimentally observed product 5-hydroxy-1-tosylindole can be formed either directly by Diels-Alder reaction of the nitropyrrole acting as alkene or by rearrangement of the dihydrooxazine N-oxides. The primary cycloadduct with the nitropyrrole acting as alkene is found to be unstable reacting further by extrusion of nitrous acid to 5-hydroxyindole. Finally, the results are compared with those obtained for the analogous furans, thiophenes, and selenophenes.

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Section: Introductionmentioning

confidence: 94%

Reactivity, Stereo- And Regioselectivity of Diels-Alder Reactions Between Five-Membered Heterocycles and Danishefsky's Diene

Brasca

Kneeteman

Mancini

et al. 2013

Proceedings of the 17th International Electronic Conference on Synthetic Organic Chemistry

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Polar Diels-Alder Reactions Under Microwave Irradiation Employing Different Heterocyclic Compounds as Electrophiles

Mancini

Ormachea

Kneeteman

2019

MROC

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During the last twenty years, our research group has been working with aromatic nitrosubstituted compounds acting as electrophiles in Polar Diels-Alder (P-DA) reactions with different dienes of diverse nucleophilicity. In this type of reaction, after the cycloaddition reaction, the nitrated compounds obtained as the [4+2] cycloadducts suffer cis-extrusion with the loss of nitrous acid and a subsequent aromatization. In this form, the reaction results are irreversible. On the other hand, the microwave-assisted controlled heating become a powerful tool in organic synthesis as it makes the reaction mixture undergo heating by a combination of thermal effects, dipolar polarization and ionic conduction. As the Diels-Alder (D-A) reaction is one of the most important process in organic synthesis, the microwave (MW) irradiation was applied instead of conventional heating, and this resulted in better yields and shorter reaction times. Several substituted heterocyclic compounds were used as electrophiles and different dienes as nucleophiles. Two experimental situations are involved: one in the presence of Protic Ionic Liquids (PILs) as solvent and the other under solvent-free conditions. The analysis is based on experimental data and theoretical calculations.

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Protic and Nonprotic Ionic Liquids in Polar Diels-Alder Reactions Using Properly Substituted Heterocycles and Carbocycles as Dienophiles. A DFT study

Mancini¹,

Ormachea²,

Rosa³

et al. 2013

Ionic Liquids - New Aspects for the Future

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Diels–Alder reactions for the rational design of benzo[b]thiophenes: DFT-based guidelines for synthetic chemists

Cited by 3 publications

References 129 publications

Reactivity, Stereo- And Regioselectivity of Diels-Alder Reactions Between Five-Membered Heterocycles and Danishefsky's Diene

Reactivity, Stereo- And Regioselectivity of Diels-Alder Reactions Between Five-Membered Heterocycles and Danishefsky's Diene

Polar Diels-Alder Reactions Under Microwave Irradiation Employing Different Heterocyclic Compounds as Electrophiles

Protic and Nonprotic Ionic Liquids in Polar Diels-Alder Reactions Using Properly Substituted Heterocycles and Carbocycles as Dienophiles. A DFT study

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