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Amide nitrogen pyramidalization changes lactam amide spinning

Author

Listed:
  • Yuko Otani

    (University of Tokyo)

  • Xin Liu

    (University of Tokyo)

  • Hisashi Ohno

    (University of Tokyo)

  • Siyuan Wang

    (University of Tokyo)

  • Luhan Zhai

    (University of Tokyo)

  • Aoze Su

    (University of Tokyo)

  • Masatoshi Kawahata

    (Tokushima Bunri University)

  • Kentaro Yamaguchi

    (Tokushima Bunri University)

  • Tomohiko Ohwada

    (University of Tokyo)

Abstract

Although cis-trans lactam amide rotation is fundamentally important, it has been little studied, except for a report on peptide-based lactams. Here, we find a consistent relationship between the lactam amide cis/trans ratios and the rotation rates between the trans and cis lactam amides upon the lactam chain length of the stapling side-chain of two 7-azabicyclo[2.2.1]heptane bicyclic units, linked through a non-planar amide bond. That is, as the chain length increased, the rotational rate of trans to cis lactam amide was decreased, and consequently the trans ratio was increased. This chain length-dependency of the lactam amide isomerization and our simulation studies support the idea that the present lactam amides can spin through 360 degrees as in open-chain amides, due to the occurrence of nitrogen pyramidalization. The tilting direction of the pyramidal amide nitrogen atom of the bicyclic systems is synchronized with the direction of the semicircle-rotation of the amide.

Suggested Citation

  • Yuko Otani & Xin Liu & Hisashi Ohno & Siyuan Wang & Luhan Zhai & Aoze Su & Masatoshi Kawahata & Kentaro Yamaguchi & Tomohiko Ohwada, 2019. "Amide nitrogen pyramidalization changes lactam amide spinning," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-018-08249-9
    DOI: 10.1038/s41467-018-08249-9
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