Amide nitrogen pyramidalization changes lactam amide spinning

Yuko Otani (), Xin Liu, Hisashi Ohno, Siyuan Wang, Luhan Zhai, Aoze Su, Masatoshi Kawahata, Kentaro Yamaguchi and Tomohiko Ohwada ()
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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

Nature Communications, 2019, vol. 10, issue 1, 1-9

Abstract: 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.

Date: 2019
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DOI: 10.1038/s41467-018-08249-9

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