Amine exchange in formamidines: An experimental and theoretical study

Marinha Df Capela, Nicholas J. Mosey, Liyan Xing, Ruiyao Wang, Anne Petitjean*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)


N-H-containing formamidines combine a reasonably strong association to carboxylic acids to form complexes of well-defined geometries with a simultaneous proton-induced electrophilicity enhancement that allows for the exchange of their amine portion. The N=C(H)-NH fragment, therefore, undergoes "imine-like" exchange with N-containing nucleophiles. Because of the prototropic equilibrium, the N=C(H)-NH fragment may behave as a "bisimine" centred on the same carbon, in which both N-containing fragments can be exchanged. Considering the proton-induced sensitisation of both C-N units and the well-defined formamidine-carboxylic acid complex geometry, it should be possible to use carboxylic acids as templates for the synthesis of defined architectures by dynamic amine exchange within formamidines. This study highlights three exchange regimes based on the nature of the incoming amine (aliphatic amines, aromatic amines and alkoxyamines), as well as exchange rules based on the amine leaving groups. Following this analysis, a proof of concept for carboxylic acid templated macrocycle formation through dynamic exchange is provided.

Original languageEnglish
Pages (from-to)4598-4612
Number of pages15
JournalChemistry - A European Journal
Issue number16
Publication statusPublished - 11 Apr 2011
Externally publishedYes


  • amidines
  • amines
  • nucleophilic substitution
  • self-assembly
  • supramolecular chemistry

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