This work was supported by the MEXT and JST, ACT-C. We thank Sachiko Nakano for her technical contribution.
Stereoelectronic Effect of Curved Aromatic Structures: Favoring the Unexpected endo Conformation of Benzylic-Substituted Sumanene†
Article first published online: 10 JUN 2013
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 52, Issue 28, pages 7314–7316, July 8, 2013
How to Cite
Higashibayashi, S., Onogi, S., Srivastava, H. K., Sastry, G. N., Wu, Y.-T. and Sakurai, H. (2013), Stereoelectronic Effect of Curved Aromatic Structures: Favoring the Unexpected endo Conformation of Benzylic-Substituted Sumanene. Angew. Chem. Int. Ed., 52: 7314–7316. doi: 10.1002/anie.201303134
- Issue published online: 4 JUL 2013
- Article first published online: 10 JUN 2013
- Manuscript Received: 15 APR 2013
- conformation analysis;
- density functional calculations;
- through-bond interactions;
- through-space interactions
Throwing a curve: The first example of a through-bond stereoelectronic effect for curved aromatic compounds is described for buckybowls, that is, benzylic-substituted sumanenes. Methyl- and hydroxysumanene favor the endo-R conformer because of a difference in the strength, between the conformers, of the hyperconjugation of the benzylic CH bond with the bowl.