This work was supported by Grants-in-Aid for Scientific Research (Nos. 22750036 and 24350023) from MEXT (Japan). H.S. also acknowledges the Toyoaki Scholarship Foundation for financial support.
Synthesis of Highly Distorted π-Extended [2.2]Metacyclophanes by Intermolecular Double Oxidative Coupling†
Article first published online: 22 APR 2013
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 52, Issue 22, pages 5740–5743, May 27, 2013
How to Cite
Koyama, Y., Hiroto, S. and Shinokubo, H. (2013), Synthesis of Highly Distorted π-Extended [2.2]Metacyclophanes by Intermolecular Double Oxidative Coupling. Angew. Chem. Int. Ed., 52: 5740–5743. doi: 10.1002/anie.201301180
- Issue published online: 17 MAY 2013
- Article first published online: 22 APR 2013
- Manuscript Received: 9 FEB 2013
- MEXT. Grant Numbers: 22750036, 24350023
- Toyoaki Scholarship Foundation
- through-space interactions
A strained relationship: Oxidation of dihydroxy-substituted acenes provides face-to-face [2.2]metacyclophane-like dimers (see scheme; O red, Si of iPr3Si groups blue). The products exhibited highly distorted structures caused by steric repulsion. UV/Vis and electrochemical analysis revealed that the HOMO–LUMO gap was decreased upon dimerization.