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Keywords:

  • amides;
  • solvolysis;
  • steric hindrance;
  • substituent effects;
  • substitution
Thumbnail image of graphical abstract

Stick or twist: By introducing steric hindrance at the nitrogen atom, stable linear amides bearing an electron-withdrawing α-substituent (Z=Ar, PhSO2, P(O)(OR)2, CN, or CO2R) can be induced to undergo solvolysis and substitution reactions through an elimination–addition mechanism (see picture). Key to this process is a low barrier to rotation around the amide bond and the α-substituent Z.