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Keywords:

  • cations;
  • hafnium;
  • hydroamination;
  • nitrogen heterocycles;
  • zirconium

Abstract

ZrIV and HfIV benzyl (neutral or cationic) and amido catalysts stabilized by pyridylamido ligands are found to be good candidates for the intramolecular hydroamination/cyclization of primary and secondary aminoalkenes. In particular, cationic monobenzyl derivatives have shown remarkable catalytic activity for the production of five and six-membered N-containing heterocycles from secondary amino alkenes. In addition, ZrIV and HfIV amido derivatives that are produced by a temperature-controlled prototropic rearrangement have provided evidence of the central role played by the metal coordination sphere in promoting such catalytic transformations efficiently.