Substituent effects on the Bergman cyclization of (Z)-1,5-hexadiyne-3-enes: A systematic computational study - Forschungsportal der Justus-Liebig-Universität Gießen:

Journalartikel

Substituent effects on the Bergman cyclization of (Z)-1,5-hexadiyne-3-enes: A systematic computational study

Autorenliste: Prall, M; Wittkopp, A; Fokin, AA; Schreiner, PR

Jahr der Veröffentlichung: 2001

Seiten: 1605-1614

Zeitschrift: Journal of Computational Chemistry

Bandnummer: 22

Heftnummer: 13

ISSN: 0192-8651

DOI Link: https://doi.org/10.1002/jcc.1114

Verlag: Wiley

Abstract:
The effects of several substituents (-BH2, -BF2, -AlH2, -CH3, -C6H5, -CN, -COCH3, -CF3, -SiH3, -NH2, -NH3+, -NO2, -PH2, -OH, -OH2+, -SH, -F, -Cl, -Br) on the Bergman cyclization of (Z)-1,5-hexadiyne-3-ene (enediyne, 3) were investigated at the Becke-Lee-Yang Parr (BLYP) density functional (DFT) level employing a 6-31G* basis set. Some of the substituents, (-NH3+, -NO2, -OH, -OH2+, -F, -Cl, -Br) are able to lower the barrier (up to a minimum of 16.9 kcal mol(-1) for difluoro-enediyne 7rr) and the reaction enthalpy (the cyclization is predicted to be exergonic for -OH2+ and -F) compared to the parent system giving rise to substituted 1,4-dehydrobenzenes at physiological temperatures.

Autoren/Herausgeber

- Uni.-Prof. Dr. Peter Richard Schreiner, PhD

Zitierstile

Harvard-Zitierstil: Prall, M., Wittkopp, A., Fokin, A. and Schreiner, P. (2001) Substituent effects on the Bergman cyclization of (Z)-1,5-hexadiyne-3-enes: A systematic computational study, Journal of Computational Chemistry, 22(13), pp. 1605-1614. https://doi.org/10.1002/jcc.1114

APA-Zitierstil: Prall, M., Wittkopp, A., Fokin, A., & Schreiner, P. (2001). Substituent effects on the Bergman cyclization of (Z)-1,5-hexadiyne-3-enes: A systematic computational study. Journal of Computational Chemistry. 22(13), 1605-1614. https://doi.org/10.1002/jcc.1114