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Keywords:

  • chalcogens;
  • isomerization;
  • nitrogen inversion;
  • selenoimidate anion;
  • selenoxo peptides
Thumbnail image of graphical abstract

Two sides to a nitrogen: The cis to trans isomerization of selenoxo peptides in alkaline conditions is rationalized in terms of rapid nitrogen inversion of the tautomeric selenoimidate anion [C(Se)[DOUBLE BOND]N[BOND]] (see scheme), which increases the isomerization rate by about 30-fold as compared to the rotational pathway of the [CSe[BOND]NH[BOND]] form. The current work identifies the imino tautomer of a selenoxo peptide bond as a potential means to enhance oligopeptide backbone dynamics in a site-specific manner.