Intramolecular self-alkylation reaction of an iron(II) dichloroclathrochelate caused cyclization–demethylation in its chelate ribbed fragment

• Iron dichloroclathrochelate undergoes a substitution with 3-dimethylaminopropylamine.
• Nucleophilic substitution gave a seven-membered N2-alicyclic ribbed chelate fragment.
• Clathrochelate product resulted from intramolecular cyclization–demethylation.

Nucleophilic substitution of an iron(II) dichloroclathrochelate precursor FeBd2(Cl2Gm)(BF)2 (where Bd2 − and Gm are α-benzildioxime dianion and glyoxime residue, respectively) with 3-dimethylaminopropylamine unexpectedly afforded the macrobicyclic product of an intramolecular cyclization followed by a demethylation reaction with elimination of CH3Cl. The molecular structure of this clathrochelate was unambiguously confirmed both in solution and in solid state using multinuclear NMR spectroscopy and by single crystal X-ray diffraction, respectively.

Nucleophilic substitution of an iron(II) dichloroclathrochelate precursor with 3-dimethylaminopropylamine gave the macrobicyclic product of intramolecular cyclization–demethylation reaction in its ribbed fragment.Figure optionsDownload as PowerPoint slide