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Possibility of [1,5] sigmatropic shifts in bicyclo[4.2.0]octa-2,4-dienes

Hannelore Goossens (UGent) , Johan Winne (UGent) , Sebastian Wouters (UGent) , Laura Hermosilla (UGent) , Pierre De Clercq (UGent) , Michel Waroquier (UGent) , Veronique Van Speybroeck (UGent) and Saron Catak (UGent)
(2015) JOURNAL OF ORGANIC CHEMISTRY. 80(5). p.2609-2620
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Abstract
The thermal equilibration of the methyl esters of endiandric acids D and E was subject to a computational study. An electrocyclic pathway via an electrocyclic ring opening followed by a ring flip and a subsequent electrocyclization proposed by Nicolaou [Nicolaou, K. C.; Chen, J. S. Chem. Soc. Rev. 2009, 38, 2993], was computationally explored. The free-energy barrier for this electrocyclic route was shown to be very close to the bicyclo[4.2.0]octa-2,4-diene reported by Huisgen [Huisgen, R.; Boche, G.; Dahmen, A.; Hechtl, W. Tetrahedron Lett. 1968, 5215]. Furthermore, the possibility of a [1,5] sigmatropic alkyl group shift of bicyclo[4.2.0]octa-2,4-diene systems at high temperatures was explored in a combined computational and experimental study. Calculated reaction barriers for an open-shell singlet biradical-mediated stepwise [1,5] sigmatropic alkyl group shift were shown to be comparable with the reaction barriers for the bicyclo[4.1.0]hepta-2,4-diene (norcaradiene) walk rearrangement. However, the stepwise sigmatropic pathway is suggested to only be feasible for appropriately substituted compounds. Experiments conducted on a deuterated analogous diol derivative confirmed the calculated (large) differences in barriers between electrocyclic and sigmatropic pathways.
Keywords
DIELS-ALDER REACTION, PERICYCLIC-REACTIONS, INITIO QUANTUM-CHEMISTRY, 2ND-ORDER PERTURBATION-THEORY, STEREOCONTROLLED TOTAL-SYNTHESIS, ENDIANDRIC ACID CASCADE, MOLECULAR-ORBITAL METHODS, MATRIX RENORMALIZATION-GROUP, ORGANIC-SYNTHESIS, AB-INITIO

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Citation

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MLA
Goossens, Hannelore et al. “Possibility of [1,5] Sigmatropic Shifts in Bicyclo[4.2.0]octa-2,4-dienes.” JOURNAL OF ORGANIC CHEMISTRY 80.5 (2015): 2609–2620. Print.
APA
Goossens, H., Winne, J., Wouters, S., Hermosilla, L., De Clercq, P., Waroquier, M., Van Speybroeck, V., et al. (2015). Possibility of [1,5] sigmatropic shifts in bicyclo[4.2.0]octa-2,4-dienes. JOURNAL OF ORGANIC CHEMISTRY, 80(5), 2609–2620.
Chicago author-date
Goossens, Hannelore, Johan Winne, Sebastian Wouters, Laura Hermosilla, Pierre De Clercq, Michel Waroquier, Veronique Van Speybroeck, and Saron Catak. 2015. “Possibility of [1,5] Sigmatropic Shifts in Bicyclo[4.2.0]octa-2,4-dienes.” Journal of Organic Chemistry 80 (5): 2609–2620.
Chicago author-date (all authors)
Goossens, Hannelore, Johan Winne, Sebastian Wouters, Laura Hermosilla, Pierre De Clercq, Michel Waroquier, Veronique Van Speybroeck, and Saron Catak. 2015. “Possibility of [1,5] Sigmatropic Shifts in Bicyclo[4.2.0]octa-2,4-dienes.” Journal of Organic Chemistry 80 (5): 2609–2620.
Vancouver
1.
Goossens H, Winne J, Wouters S, Hermosilla L, De Clercq P, Waroquier M, et al. Possibility of [1,5] sigmatropic shifts in bicyclo[4.2.0]octa-2,4-dienes. JOURNAL OF ORGANIC CHEMISTRY. 2015;80(5):2609–20.
IEEE
[1]
H. Goossens et al., “Possibility of [1,5] sigmatropic shifts in bicyclo[4.2.0]octa-2,4-dienes,” JOURNAL OF ORGANIC CHEMISTRY, vol. 80, no. 5, pp. 2609–2620, 2015.
@article{5944624,
  abstract     = {The thermal equilibration of the methyl esters of endiandric acids D and E was subject to a computational study. An electrocyclic pathway via an electrocyclic ring opening followed by a ring flip and a subsequent electrocyclization proposed by Nicolaou [Nicolaou, K. C.; Chen, J. S. Chem. Soc. Rev. 2009, 38, 2993], was computationally explored. The free-energy barrier for this electrocyclic route was shown to be very close to the bicyclo[4.2.0]octa-2,4-diene reported by Huisgen [Huisgen, R.; Boche, G.; Dahmen, A.; Hechtl, W. Tetrahedron Lett. 1968, 5215]. Furthermore, the possibility of a [1,5] sigmatropic alkyl group shift of bicyclo[4.2.0]octa-2,4-diene systems at high temperatures was explored in a combined computational and experimental study. Calculated reaction barriers for an open-shell singlet biradical-mediated stepwise [1,5] sigmatropic alkyl group shift were shown to be comparable with the reaction barriers for the bicyclo[4.1.0]hepta-2,4-diene (norcaradiene) walk rearrangement. However, the stepwise sigmatropic pathway is suggested to only be feasible for appropriately substituted compounds. Experiments conducted on a deuterated analogous diol derivative confirmed the calculated (large) differences in barriers between electrocyclic and sigmatropic pathways.},
  author       = {Goossens, Hannelore and Winne, Johan and Wouters, Sebastian and Hermosilla, Laura and De Clercq, Pierre and Waroquier, Michel and Van Speybroeck, Veronique and Catak, Saron},
  issn         = {0022-3263},
  journal      = {JOURNAL OF ORGANIC CHEMISTRY},
  keywords     = {DIELS-ALDER REACTION,PERICYCLIC-REACTIONS,INITIO QUANTUM-CHEMISTRY,2ND-ORDER PERTURBATION-THEORY,STEREOCONTROLLED TOTAL-SYNTHESIS,ENDIANDRIC ACID CASCADE,MOLECULAR-ORBITAL METHODS,MATRIX RENORMALIZATION-GROUP,ORGANIC-SYNTHESIS,AB-INITIO},
  language     = {eng},
  number       = {5},
  pages        = {2609--2620},
  title        = {Possibility of [1,5] sigmatropic shifts in bicyclo[4.2.0]octa-2,4-dienes},
  url          = {http://dx.doi.org/10.1021/jo5027639},
  volume       = {80},
  year         = {2015},
}

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