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Oxidative Cyclodimerization After Tandem Cyclization of Dehydrobenzo[14]annulenes Induced by Alkyllithium

Authors

  • Shunpei Nobusue,

    1. Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)
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  • Dr. Akihiro Shimizu,

    1. Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)
    2. Present address: Department of Synthetic and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto (Japan)
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  • Prof. Kenji Hori,

    1. Division of Material Sciences, Graduate School of Science and Engineering, Yamaguchi University, Yamaguchi (Japan)
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  • Dr. Ichiro Hisaki,

    1. Department of Material and Life Science, Graduate School of Engineering, Osaka University, Osaka (Japan)
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  • Prof. Mikiji Miyata,

    1. Department of Material and Life Science, Graduate School of Engineering, Osaka University, Osaka (Japan)
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  • Prof. Yoshito Tobe

    Corresponding author
    1. Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)
    • Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)
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  • This work was supported by a The Grants-in-Aid for Scientific Research on Innovative Areas “Organic Synthesis based on Reaction Integration” (No. 2105). The synchrotron radiation experiments were performed at the BL38B1 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal No. 2009B1969 and 2010A1427). We are grateful to Dr. K. Miura, Dr. S. Baba, and Dr. N. Mizuno for crystallographic data collection, and Prof. Kendall N. Houk of the University of California, Los Angeles for his advice on the theoretical studies.

Abstract

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After eight: Reactions of dehydrobenzo[14]annulenes induced by the addition of n-butyllithium led to the discovery of an unprecedented oxidative cyclodimerization, which forms eight-membered ring products in up to 30 % yield. The product contains two indeno[2,1-a]fluorene components connected by a single and a double bond, which result from three transannular bond formations.

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