Synthesis of Highly Distorted π-Extended [2.2]Metacyclophanes by Intermolecular Double Oxidative Coupling

Authors

  • Yutaro Koyama,

    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
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  • Dr. Satoru Hiroto,

    Corresponding author
    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
    • Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)

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  • Prof. Dr. Hiroshi Shinokubo

    Corresponding author
    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
    • Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)

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  • 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.

Abstract

original image

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.

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