Mechanism of the Diels-Alder reaction:  reactions of butadiene with ethylene and cyanoethylenes

Dewar, Michael J. S.; Olivella, Santiago; Stewart, James J. P.

doi:10.1021/ja00279a018

Cited by 306 publications

(148 citation statements)

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“…Analysis of the points along the IRCs shows that these cycloaddition reactions are concerted two-stage processes. [25] In the first stage, the C4-C5 bond is completely formed in the nucleophilic attack of the C5 position of 1-vinylpyrrolidine on the C4 carbon atom of nitrosoethylene. The O1-C6 bond is formed in the second stage of the reaction.…”

Section: Dft Analysis Based On the Reactivity Indexesmentioning

confidence: 99%

Towards an Understanding of the Polar Diels–Alder Reactions of Nitrosoalkenes with Enamines: A Theoretical Study

2006

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The polar Diels-Alder reactions of nitrosoalkenes with enamines have been studied using DFT methods at the B3LYP/ 6-31G* level of theory. These Diels-Alder reactions are characterized by a nucleophilic attack of the enamine at the conjugated position of the nitrosoalkene with concomitant ringclosure. The reactions present a total regioselectivity and a large endo selectivity. The analysis, based on the global electrophilicity of the reagents in the ground state, the natural bond orbital (NBO), and the topological analysis of the elec-

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Section: Dft Analysis Based On the Reactivity Indexesmentioning

confidence: 99%

Towards an Understanding of the Polar Diels–Alder Reactions of Nitrosoalkenes with Enamines: A Theoretical Study

2006

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“…[1] This reaction has been extensively investigated using experimental [2][3][4][5][6] and theoretical [7][8][9][10][11][12][13][14][15][16][17][18] methods. Synchronous and asynchronous concerted or nonconcerted mechanisms have been discussed in the literature.…”

Section: Introductionmentioning

confidence: 99%

The Diels–Alder Reaction of Ethene and 1,3‐Butadiene: An Extended Multireference ab initio Investigation

2004

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The concerted and stepwise mechanisms of the Diels-Alder reaction between 1,3-butadiene and ethene have been investigated using highly correlated multireference methods (MRAQCC) and extended basis sets. Full MRAQCC geometry optimizations have been performed in all cases. The best estimate for the energy barrier of the Diels-Alder reaction is 22 kcalmol(-1). Anti- and gauche-out minima for the biradical structures and corresponding fragmentation saddle points have been determined. The biradical anti fragmentation saddle point is located 6.5 kcalmol(-1) above the concerted saddle point. The gauche-in structure does not correspond to a local minimum, but leads on geometry optimization directly to cyclohexene.

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“…Theoretical calculations can be important in situations of this kind, and a number of calculations for Diels-Alder reactions have been reported. [2][3][4][5][6][7][8] Computer technologies advances in quantum chemistry provide an opportunity to explore the theoretical aspects of some chemical reactions. [6][7][8] And use of these kind technologies provides a significant aid in the experimental studies to elucidate the mechanism of DielsAlder reaction.…”

Section: Introductionmentioning

confidence: 99%

“…There are many studies 2,3,5,12 where authors by different methods of calculations obtain information about the mechanism of these kind reactions. In the article, 5 authors suggest that Diels-Alder reactions in general proceed via very unsymmetrical transition states, close to biradicals in structure and with energies differing little from those of the corresponding biradicals.…”

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confidence: 99%

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Quantum chemical study of reaction mechanism of [4+2]-cycloaddition between 2,3-dimethylbuta-1,3-diene and methyl acrylate

Kovalskyi¹,

Маршалок²,

Vytrykush³

et al. 2017

10.5267/j.ccl

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The quantum-chemical modeling mechanism of the [4+2]-cycloaddition reaction of 2,3 dimethylbuta-1,3-diene and methyl acrylate was conducted. Its qualitative aspects were analyzed at the molecular level by the program MOPAC2012 and semiempirical method RM1. The potential energy surfaces of 2,3 dimethylbuta-1,3-diene and methyl acrylate [4+2] cycloaddition possible reaction pathways were constructed by restricted and unrestricted Hartree-Fock approximation. It has been established that the molecule of the final product methyl-3,4-dimethylcyclohex-3-encarboxylate has the half-chair shape, wherein the carboalkoxyl group is in the exo-orientation. Interaction between molecules of 2,3 dimethylbuta-1,3-diene and methyl acrylate occurs by a two-step mechanism more likely than one-step, since the activation parameters of this interaction maximum coincide with the experimental data.

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Mechanism of the Diels-Alder reaction: reactions of butadiene with ethylene and cyanoethylenes

Cited by 306 publications

References 0 publications

Towards an Understanding of the Polar Diels–Alder Reactions of Nitrosoalkenes with Enamines: A Theoretical Study

Towards an Understanding of the Polar Diels–Alder Reactions of Nitrosoalkenes with Enamines: A Theoretical Study

The Diels–Alder Reaction of Ethene and 1,3‐Butadiene: An Extended Multireference ab initio Investigation

Quantum chemical study of reaction mechanism of [4+2]-cycloaddition between 2,3-dimethylbuta-1,3-diene and methyl acrylate

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