A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Cui, Cheng‐Xing; Liu, Yajun

doi:10.1002/poc.3313

Cited by 22 publications

(22 citation statements)

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“…The interconversion of trans ‐1,3‐butadiene and cis ‐1,3‐butadiene has been thoroughly discussed in our previous research . Here, we concentrate on the interconversion of the trans and cis products of the C 60 and C 70 reactions.…”

Section: Resultssupporting

confidence: 53%

“…from trans P to PTS to cis P, reflecting that the degrees of freedom were nearly unchanged during the process. Because the energy barriers of the reactions from trans Ps to cis Ps are not very high, and the processes are all exothermic and exergonic by a large extent, we can obtain a process from the reactants of trans ‐1,3 butadiene and fullerene to cis Ps, which are similar to that of the iconic DA reaction . The process can be written as trans ‐1,3‐butadiene and fullerenes → trans TSs → trans Ps → biradical PTSs → cis Ps.…”

Section: Resultsmentioning

confidence: 99%

“…The DA reaction between the trans form of 1,3‐butadiene with ethylene is possible, although conventional view argues that this reaction is limited in the cis form of diene with dienophile . There is a close relation between the DA cycloadditions of cis and trans forms of 1,3‐butadiene to ethylene . In the current project, we theoretically investigated the reactions of trans ‐1,3‐butadiene and all types of bonds in C 60 or C 70 and compared them with the results regarding the cis form.…”

Section: Introductionmentioning

confidence: 99%

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A DFT study on Diels-Alder cycloadditions oftrans-1,3-butadiene to C₆₀and C₇₀

Cui

Liu

2014

J. Phys. Org. Chem.

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Investigation of the relative reactivity of bonds in fullerenes will provide fundamental theory for the design of fullerenebased materials. We have theoretically investigated the reactivity of the Diels-Alder (DA) cycloaddition of cis-1,3-butadiene to all types of bonds in C 60 and C 70 using the M06-2X hybrid density functional theory (DFT) calculations (J. Phys. Org. Chem. 2012, 25 850-855) and have pointed out that the DA cycloadditions of cis and trans forms of 1,3-butadiene to ethylene have a specially intimate relationship (J. Phys. Org. Chem. 2014, 27 652-660). For the aim of telling a whole story of the DA cycloaddition concerning C 60 and C 70 , the DA cycloadditions of trans-1,3-butadiene to all types of bonds in C 60 and C 70 were explored at the same theoretical level as those of the cis-1,3-butadiene. The calculated results related with the trans-and cis-1,3-butadienes were compared. The potential energy curves of DA cycloadditions of trans-and cis-1,3-butadiene to C 60 and C 70 were discussed. The distortion-interaction energy model was employed to elucidate the origin of different reactivity of all kinds of C-C bonds. The solvent effects were examined using the continuum solvent model. These current results, along with our previous research, will help to obtain an overall view of the DA cycloadditions of 1,3-butadiene to C 60 and C 70 . Copyright

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Section: Resultssupporting

confidence: 53%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A DFT study on Diels-Alder cycloadditions oftrans-1,3-butadiene to C₆₀and C₇₀

Cui

Liu

2014

J. Phys. Org. Chem.

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“…[22][23][24] We found M06-2X is believable for some typical DA reactions. [25][26][27] A polarized double-ζ (6-31G(d,p)) basis set was used for all atoms. All the geometries along the reaction coordinate were full optimized without any restriction.…”

Section: Computational Detailsmentioning

confidence: 99%

Regioselectivity and stereoselectivity of Diels-Alder reaction: a DFT study on the functionalization of organic semiconductor crystals

Cui

Liu

2016

J. Phys. Org. Chem.

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Diels–Alder (DA) reaction is one of the most commonly tools in functionalizing organic semiconductor crystals. The DA reactions of two organic semiconductors, i.e. tetracene (1) and rubrene (2), to several dienophiles (3 to 7) were performed experimentally recently. But the kinetics and mechanism of stereoselectivity and regioselectivity remain unknown. In the current study, all related 20 DA reactions (totally 32 possible pathways) were investigated by density functional theory. It was found that the reaction of 7 and a–b position of 1 is the most favorable one. The c–d position of 2 is more reactive than its a–b position when 2 combines with 3, but is less reactive when combines with 4 to 7. The endo and exo pathways have similar activation barriers in each reaction. The rate coefficients were calculated using the canonical variational transition state theory and their Arrhenius expressions were fitted. The theoretical conclusion agrees with the experimental observations and is of general importance for similar reactions. Solvent has a slight effect on these reactions. Copyright © 2016 John Wiley & Sons, Ltd.

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“…[8][9][10][11][12][13][14][15] Generally, the classic D-A cycloadditions are reacted by electronic-decient diene and electronic-rich dienophile synergetically. [16][17][18][19] However, there are a series of untraditional D-A reactions [20][21][22][23][24][25][26][27][28][29][30][31] between electronically mismatched components, such as the addition between 1,3-butadiene and ethylene (both electron-decient components) or trans-1,3-butadiene and C60 or C70 (both electron-rich components). This novel D-A reaction always exhibits excellent selectivity but also requires stricter conditions than those of the traditional D-A reaction, where the components of dienes and dienophiles generally experience different transformations in order to satisfy the requirement of D-A reaction through the formation of free radical ions, 20,21 molecular electrical reversal [22][23][24][25] and polarity reversal.…”

Section: Introductionmentioning

confidence: 99%