A Computational Study of the Thermal Cycloreversion of 2,2,6-Trimethyl-4H-1,3-dioxin-4-one and a Related Species: Retro-Diels-Alder Reaction or Concerted Nucleophilic Attack?

1995 ◽  
Vol 60 (12) ◽  
pp. 3736-3742 ◽  
Author(s):  
Shawn W. E. Eisenberg ◽  
Mark J. Kurth ◽  
William H. Fink
Keyword(s):  
Related Species ◽  
Computational Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Nucleophilic Attack ◽  
Diels Alder Reaction

QTAIM–DI–VISAB computational study on the Diels–Alder reaction of cyclopentadiene — On the nature of the so-called secondary orbital interactions

2008 ◽  
Vol 86 (7) ◽  
pp. 737-744 ◽  
Author(s):  
Nick Henry Werstiuk ◽  
Wojciech Sokol
Keyword(s):  
Computational Study ◽  
Transition States ◽  
Alder Reaction ◽  
Diels Alder ◽  
Physical Organic Chemistry ◽  
Hydrogen Atoms ◽  
Endo Isomer ◽  
Orbital Interactions ◽  
Physical Organic ◽  
Diels Alder Reaction

We have undertaken a QTAIM–DI–VISAB computational study of the dimerization of cyclopentadiene (1), the archetypal example of a Diels–Alder reaction that has been studied experimentally and computationally. Secondary orbital interactions (SOIs) that have gained acceptance in the interpretation of stereoselectivities seen in many cycloaddition reactions have been used to account for the fact that the endo isomer was the kinetic product of the reaction. To this point, “classical” MO analyses along with a variety of arbitrarily assigned solid and dashed lines (solid lines and bold dashes for “primary” interactions and dashed and dotted lines to differentiate between different SOI schemes) have been used in an attempt to describe the bonding of the transition states. Yet, the existence of SOIs has been challenged. Our interest in applying QTAIM to fundamental chemical problems in physical organic chemistry, with the goal of refining our knowledge of the bonding in transition-states and ground-state molecules while obviating the need to use a variety of confusing arbitrarily assigned dashed and dotted lines, led us to a QTAIM–DI–VISAB computational study of the endo and exo dimerizations of 1 at the DFT B3PW91 and MPW1PW91 levels. We have characterized the bonding interactions between cyclopentadiene rings in the various transition states and show that “normal” bonds are present where SOIs have been considered to exist. There is no need to use different types of dashed and dotted lines. An analysis of the changes in atom energies revealed that the significant destabilization of the carbon atoms in achieving the TSs (potentially leading to a very high barrier) is ameliorated by a stabilization of the hydrogen atoms leading to the relatively low barrier for the D–A reaction.Key words: cyclopentadiene dimerization, bispericyclic transition states, DFT calculations, QTAIM–DI–VISAB analysis, bonding, atom energy analysis.

scholarly journals A Computational Study of the Relative Aromaticity of Pyrrole, Furan, Thiophene and Selenophene, and Their Diels-Alder Stereoselectivity

2020 ◽  
Author(s):  
Veejendra Yadav
Keyword(s):  
Computational Study ◽  
Lone Pair ◽  
Alder Reaction ◽  
Diels Alder ◽  
Size Mismatch ◽  
Aromatic Character ◽  
Diels Alder Reaction ◽  
Ground State Structures ◽  
Better Than

The collinearity of terminal <i>p</i> orbitals of a diene with that of a dienophile is required for an effective overlap to result in s bond formation during the Diels-Alder reaction. The ease of the DA reaction of a cyclic diene with a given dienophile, therefore, must also depend on the distance between the termini of the diene. A distance larger than the unsaturated bond of the dienophile is expected to raise the energy of activation. This scenario has been amply demonstrated from the study of reactions of several dienes, some designed to serve the purpose, with different dienophiles. The five-ring heterocycles pyrrole, furan, thiophene and selenophene possess varying aromatic character for the varied resonance participation of the heteroatom lone pair with ring p bonds. The aromaticity decreases in the same order due to: (a) the increasing s<sub>C-X</sub> (X = heteroatom) bond length lifts the bond uniformity required for ring current, hence aromaticity, such as in benzene and (b) size-mismatch of the interacting lone pair orbital and the ring <i>p</i> orbitals, especially in thiophene and selenophene, both allowing poor overlap in the ground state structures. It is demonstrated that increase alone in the activation energies of the DA reactions of pyrrole, furan, thiophene and selenophene cannot be considered a measure of relative aromaticity as often done and even theoretically attempted in many ways to prove just that. The separation of the termini of the diene has a much larger role in the determination of activation energy, especially in thiophene and selenophene, than their aromaticity profile. There cannot be a measure better than the relative intensity of heteroatom lone pair overlap with ring p bonds, giving rise to a six-electron like system in following Hückel’s 4n+2 rule, to assess the relative aromaticity.

Strained Allenes as Dienophiles in the Diels−Alder Reaction:  An Experimental and Computational Study

1999 ◽  
Vol 64 (3) ◽  
pp. 976-983 ◽  
Author(s):  
Maja Nendel ◽  
Laren M. Tolbert ◽  
Laura E. Herring ◽  
Md. Nurul Islam ◽  
K. N. Houk
Keyword(s):  
Computational Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Synthesis of bicyclic diones and thiones. Facile methylation of the enolates of bicyclo[2.2.1]heptane-2,5-dione and bicyclo[2.2.2]octane-2,5-dione. An AM1 computational study of bicyclic enolates

1992 ◽  
Vol 70 (3) ◽  
pp. 974-980 ◽  
Author(s):  
N. H. Werstiuk ◽  
S. Yeroushalmi ◽  
Hong Guan-Lin
Keyword(s):  
Raney Nickel ◽  
Good Yield ◽  
Computational Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Am1 Calculations ◽  
Diels Alder Reaction ◽  
Bicyclic Ketones ◽  
One Step

A group of bicyclic ketones and thiones have been synthesized for homenolization studies. Bicyclo[2.2.1]heptane-2,5-dione (6) undergoes unusually rapid tetramethylation giving 3,3,6,6-tetramethylbicyclo[2.2.1]heptane-2,5-dione (1) in good yield. Treatment of 1 with P2S5 in xylene gave 3,3,6,6-tetramethylbicyclo[2.2.1]heptane-2,5-dithione (2) and 3,3,6,6-tetramethyl 15-oxo-bicyclo[2.2.1]heptane-2-thione (3), which was converted into 4 with Raney nickel. Bicyclo[2,2,2]octane-2,5-dione (7), prepared via a Diels–Alder reaction between 2-trimethylsilyloxy-1,3-cyclohexadiene and and α-acetoxyacrylonitrile followed by a one-step desilylation/hydrolysis, also undergoes facile tetramethylation giving 3,3,6,6-tetramethylbicyclo[2.2.2]octane-2,5-dione (5) in good yield. AM1 calculations were carried out on the α-enolates of bicyclo[2.2.1]heptan-2-one, 6, 5-methylidenebicyclo[2.2.1]heptan-2-one, and 4-acetylbicyclo[2.2.1]-heptan-2-one in an attempt to gain information on the source of the enhanced acidity of the C-3 hydrogens of 6 and 7. Keywords: bicyclic ketones, thiones, synthesis.

Hetero Diels−Alder Reaction of Vinyl Allenes and Aldehydes. An Experimental and Computational Study

2006 ◽  
Vol 71 (24) ◽  
pp. 9153-9164 ◽  
Author(s):  
David Regás ◽  
Juan M. Ruiz ◽  
María M. Afonso ◽  
J. Antonio Palenzuela
Keyword(s):  
Computational Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

scholarly journals Synthesis of polycyclic phosphonates via an intramolecular Diels-Alder reaction of 2-benzoylbenzalaldehyde and alkenyl phosphites

2019 ◽  
Vol 25 (1) ◽  
pp. 73-77
Author(s):  
Kenji Yamana ◽  
Hirofumi Nakano
Keyword(s):  
Lewis Acid ◽  
Alder Reaction ◽  
Diels Alder ◽  
Nucleophilic Attack ◽  
Carbonyl Carbon ◽  
Diels Alder Reaction

AbstractIn this paper, we present a Lewis-acid-promoted reaction of 2-benzoylbenzaldehyde and trialkenyl phosphites, which resulted in the formation of polycyclic phosphonates. The reaction proceeded via nucleophilic attack of trialkenyl phosphite on the carbonyl carbon of 2-benzoylbenzaldehyde. The subsequent intramolecular Diels-Alder reaction led to the formation of the cyclic phosphonate.

On the Mechanism of Conversion of Substituted Glycals to Chiral Acenes via Diels- Alder Reaction: A Computational Study

2021 ◽  
Author(s):  
Kalyanashis Jana ◽  
Padmaja D. Wakchaure ◽  
Nazar Hussain ◽  
Debaraj Mukherjee ◽  
Bishwajit Ganguly
Keyword(s):  
Computational Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Aromatic Systems

Synthesis of linearly fused aromatic systems using glycal-based diene with an aryne is a long-standing interest in glycal chemistry. We have examined the mechanistic pathways for the transformation of substituted...

Density functional theory computational study on Diels–Alder reactions of cyclopentadiene with selected vinylsilanes and methylenecyclopropane

2011 ◽  
Vol 89 (3) ◽  
pp. 409-414 ◽  
Author(s):  
Nick Henry Werstiuk ◽  
Wojciech Sokol
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Computational Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Rate Data ◽  
Synthetic Route ◽  
Functional Theory ◽  
Diels Alder Reaction

Aimed at predicting relative reactivities, density functional theory (DFT) calculations were carried out on a series of Diels–Alder reactions involving silylvinyl derivatives reacting with cyclopentadiene as part of a synthetic research project. Using three reactions for which experimental rate data are available to calibrate our calculations, we computationally pinpointed the best synthetic route to bicyclo[2.2.1]hept-5-ene-2,2-diylbis(trimethylsilane) (1). The synthesis begins with the Diels–Alder reaction of cyclopentadiene (2) with commercially available (1-bromovinyl)trimethylsilane (6).

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