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Photoinduced electron-transfer reaction of α-bromomethyl-substituted benzocyclic β-keto esters with amines: selective reaction pathways depending on the nature of the amine radical cations

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Abstract

Photoinduced electron-transfer reaction of α-bromomethyl-substituted benzocyclic β-keto esters with tertiary amines was investigated. Debrominated β-keto esters and ring-expanded γ-keto esters were obtained as major products. On the basis of mechanistic experiments it was concluded that these products are formed via a reaction sequence of selective carbon–bromine bond cleavage and subsequent competitive hydrogen abstraction and Dowd–Beckwith ring-expansion of the resulting primary alkyl radicals. The characteristic product distribution observed for the type of amine used is rationalized on the basis of selective reaction pathways of generated radical intermediates that depend on the nature of the amine radical cations.

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Acknowledgments

This work was partly supported by Grants-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan. We thank Dr Yukiko Matsumura (Tokyo Institute of Technology) for her assistance with elemental analysis and high-resolution mass spectroscopy of some of the compounds reported. We thank Professor James M. Tanko (Virginia Polytechnic Institute and State University, USA) for his help with editing of the manuscript. The assistance of Mr Tsuneaki Hoshi with preparation of the manuscript is also acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Niigata University, Ikarashi-2, 8050, Niigata, 950-2181, Japan

    Eietsu Hasegawa, Emi Tosaka, Akira Yoneoka, Yukinobu Tamura & Shin-ya Takizawa

  2. Institute for Molecular Science, Myodaiji, Okazaki, 444-8585, Japan

    Masaaki Tomura

  3. Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8502, Japan

    Yoshiro Yamashita

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  1. Eietsu Hasegawa
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Correspondence to Eietsu Hasegawa.

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Hasegawa, E., Tosaka, E., Yoneoka, A. et al. Photoinduced electron-transfer reaction of α-bromomethyl-substituted benzocyclic β-keto esters with amines: selective reaction pathways depending on the nature of the amine radical cations. Res Chem Intermed 39, 247–267 (2013). https://doi.org/10.1007/s11164-012-0646-2

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