Design and synthesis of a tetradentate '3-amine-1-carboxylate' ligand to mimic the metal binding environment at the non-heme iron(II) oxidase active site.
Non-heme iron(II) oxidases (NHIOs) catalyse a diverse array of oxidative chemistry in Nature. As part of ongoing efforts to realize biomimetic, iron-mediated C-H activation, we report the synthesis of a new 'three-amine-one-carboxylate' ligand designed to complex with iron(II) and mimic the NHIO active site. The tetradentate ligand has been prepared as a single enantiomer in nine synthetic steps from N-Cbz-L-alanine, pyridine-2,6-dimethanol and diphenylamine, using Seebach oxazolidinone chemistry to control the stereochemistry. X-Ray crystal structures are reported for two important intermediates, along with variable temperature NMR experiments to probe the hindered interconversion of conformational isomers of several key intermediates, 2,6-disubstituted pyridine derivatives. The target ligand and an N-Cbz-protected precursor were each then complexed with iron(II) and tested for their ability to promote alkene dihydroxylation, using hydrogen peroxide as the oxidant.
School of Chemistry F11, The University of Sydney, NSW 2006, Australia.
Victoria J
VJ
Dungan
Yannick
Y
Ortin
Helge
H
Mueller-Bunz
Peter J
PJ
Rutledge
D000475:Alkenes / Q000737:chemistry; D000588:Amines / Q000138:chemical synthesis / Q000737:chemistry*; D001665:Binding Sites; D032701:Biomimetics; D002264:Carboxylic Acids / Q000138:chemical synthesis / Q000737:chemistry*; D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D007501:Iron / Q000378:metabolism*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D023303:Oxazolidinones / Q000138:chemical synthesis / Q000737:chemistry; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000378:metabolism
D000475:Alkenes; D000588:Amines; D002264:Carboxylic Acids; D008024:Ligands; D023303:Oxazolidinones; D007501:Iron; D010088:Oxidoreductases