Endo preference in the Diels-Alder cycloaddition of butadiene and maleic anhydride

Stephenson, L. M.; Smith, D. E.; Current, Steven

doi:10.1021/jo00142a035

Cited by 40 publications

(32 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…However, the electronic factor shows a poor correlation with the endo–exo selectivity trend. For unsubstituted CP, Δ G act (endo) is 2.07 kcal/mol less than Δ G act (exo), which means an overestimated endo preference compared with the experimental results . Δ G act (endo) for XOH is obviously deviated from the trend line and results in a slight exo preference (Δ G act (exo‐endo) −0.15 kcal/mol).…”

Section: Resultssupporting

confidence: 92%

See 1 more Smart Citation

Substituent effects in the Diels–Alder reactions of butadienes, cyclopentadienes, furans and pyroles with maleic anhydride

Qiu

2015

J of Physical Organic Chem

View full text Add to dashboard Cite

In this study, activation energies in the Diels–Alder reactions of a series of substituted butadienes, cyclopentadienes, furans and pyroles with maleic anhydride were calculated by the M06‐2X/6‐31G(d) method. The substituent effects on the reactivity and the endo–exo selectivity have been examined. The strength of reactivity effect has an order of pyroles > furans > cyclopentadienes > butadienes, which is highly correlated with the lowest unoccupied molecular orbital energy, the electronic chemical potential and the electrophilicity of parent diene but relatively less correlated with the highest occupied molecular orbital energy and chemical hardness. The trend that an increase of necleophilicity caused by an electron‐donating group on the diene favors the endo TS is effective with C2 substitution. With C1 substitution, the trend is ambiguous or even opposite. Copyright © 2015 John Wiley & Sons, Ltd.

show abstract

Section: Resultssupporting

confidence: 92%

“…For the parent BD, the exo and endo TSs result in a same cycloadduct, but Δ G act (endo) is less than Δ G act (exo) by 2.37 kcal/mol. It has been found previously that the reaction of deuterium‐labeled BD with MA reveals an 85/15 preference for endo adducts (Δ G act (exo‐endo) ~1.2 kcal/mol) …”

Section: Resultsmentioning

confidence: 70%

Substituent effects in the Diels–Alder reactions of butadienes, cyclopentadienes, furans and pyroles with maleic anhydride

Qiu

2015

J of Physical Organic Chem

View full text Add to dashboard Cite

show abstract

“…The regioselectivity takes place under kinetic control, in view of the higher activation barrier computed for the formation of the exo cycloadduct. Our calculated M05‐2X/def2‐TZVPP activation energy difference (ΔΔ G ‡ 298 = 2.1 kcal/mol) is in very good agreement with the available experimental value of 2.5 kcal/mol (measured at 298 K), which supports the selected computational methodology for the present study (Supporting Information).…”

Section: Resultssupporting

confidence: 87%

“…Indeed, the [4 1 2] cycloaddition reaction between s-cis-butadiene and MA is reported to proceed with a lower endoselectivity (experimental DDG ‡ 298 5 1.2 kcal/mol at 353 K). [29] Our activation strain analyses confirm that the reduced endo selectivity stems from a smaller difference in the strain curves of endo pathways and exo pathways while the interaction curves show a similar behavior as in the case of CP (see Fig. 3, right).…”

Section: Full Papersupporting

confidence: 75%

“…The above findings suggest that the endo selectivity can be reduced by avoiding the unfavorable steric arrangement that occurs between the methylene and oxygen moieties of CP and MA, for example, by using s‐cis ‐butadiene instead of cylcopentadiene. Indeed, the [4 + 2] cycloaddition reaction between s‐cis ‐butadiene and MA is reported to proceed with a lower endoselectivity (experimental

Δ Δ G_{298}^{‡}

= 1.2 kcal/mol at 353 K) …”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Origin of the “endo rule” in Diels-Alder reactions

Fernández

Bickelhaupt

2013

J. Comput. Chem.

View full text Add to dashboard Cite

Detailed density functional theory calculations definitively rationalize the preference for the endo cycloadduct (also known as endo rule) in text-book thermal Diels-Alder reactions involving maleic anhydride and cyclopentadiene or butadiene. This selectivity is mainly caused by an unfavorable steric arrangement in the transition-state region of the exo pathway which translates into a more destabilizing activation strain. In contrast with the widely accepted, orbital-interaction-based explanation for the endo rule, it is found that neither the orbital interactions nor the total interaction between the deformed reactants contributes to the endo selectivity.

show abstract

Intramolekulare Diels-Alder-Reaktion vom Typ 2: Synthese und Chemie von Brückenkopf-Alkenen

2001

View full text Add to dashboard Cite

Sparks wurde 1972 geboren und wuchs in Stockbridge, Massachusetts, auf. Er erhielt seinen BSc 1995 am Rensselaer Polytechnic Institute, wobei er ein einjähriges Forschungspraktikum bei Burroughs Wellcome in der Abteilung für Organische Chemie absolvierte. Nach einem Jahr als Forschungslaborant bei Albany Molecular Research begann er seine Doktorarbeit an der UCI unter Anleitung von Professor Kenneth J. Shea. Zu seinen Forschungsinteressen gehört die Entwicklung von Hetero-Diels-Alder-Typ-2-Reaktionen und die Naturstoffsynthese. Kenneth J. Shea wurde in Queens im Staat New York geboren. Er erhielt den BSc und den MSc in Chemie von der University of Toledo. Seine Doktorarbeit führte er auf dem Gebiet der Physikalischen Organischen Chemie an der Pennsylvania State University durch. Nach einem Postdoc-Aufenthalt am California Institute of Technology wurde er 1974 Professor an der University of California in Irvine. Seine Forschungsinteressen sind auf präparative und mechanistische Organische Chemie, auf Polymerchemie und auf Materialforschung gerichtet. B. R. Bear K. J. Shea S. M. Sparks Schema 1. Vorschlag für eine Reaktionskaskade, die von 1 zu 3 führt.

show abstract

Endo preference in the Diels-Alder cycloaddition of butadiene and maleic anhydride

Cited by 40 publications

References 2 publications

Substituent effects in the Diels–Alder reactions of butadienes, cyclopentadienes, furans and pyroles with maleic anhydride

Substituent effects in the Diels–Alder reactions of butadienes, cyclopentadienes, furans and pyroles with maleic anhydride

Origin of the “endo rule” in Diels-Alder reactions

Intramolekulare Diels-Alder-Reaktion vom Typ 2: Synthese und Chemie von Brückenkopf-Alkenen

Contact Info

Product

Resources

About