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Mechanism of photoisomerization of optically pure trans-2,3-diphenylcyclopropane-1-carboxylic acid derivatives

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Abstract

The photochemistry of optically pure isomers of α-methylbenzylamide of trans-2,3-diphenylcyclopropane-1-carboxylic acid has been examined in isotropic solution and within zeolites. The results suggest that these isomerize through cleavage of C2–C3 bond. The direct excitation in solution leads to non-equilibrating 1,3-singlet diradical intermediates whereas triplet sensitization results in equilibrating 1,3-triplet diradical intermediates. The direct excitation within NaY zeolite seems to result in equilibrating zwitterionic intermediates. Studies on the optically pure trans isomers allow one to understand the mechanism of chiral induction during the photoisomerization of mesocis-2,3-diphenylcyclopropane-1-carboxylic acid. The current study has clarified the nature of the excited states involved during the classic (R)-N-acetyl-1-naphthylethylamine sensitized isomerization of 1,2-diphenylcyclopropane.

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Authors and Affiliations

  1. Department of Chemistry, Tulane University, New Orleans, LA, 70118, USA

    J. Sivaguru & V. Ramamurthy

  2. Department of Molecular Chemistry and PRESTO (JST), Osaka University, 2-1 Yamada-oka, Suita, 565-0871, Japan

    Takehiko Wada & Yoshihisa Inoue

  3. ICORP Entropy Control Project, JST, 4-6-3 Kamishinden, Toyonaka, 560-0085, Japan

    Yumi Origane & Yoshihisa Inoue

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  1. J. Sivaguru
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  2. Takehiko Wada
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  5. V. Ramamurthy
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Correspondence to V. Ramamurthy.

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Dedicated to Professor Hiroshi Masuhara on the occasion of his 60th birthday

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Sivaguru, J., Wada, T., Origane, Y. et al. Mechanism of photoisomerization of optically pure trans-2,3-diphenylcyclopropane-1-carboxylic acid derivatives. Photochem Photobiol Sci 4, 119–127 (2005). https://doi.org/10.1039/b410480c

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