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.
Dungan
Victoria J
VJ
School of Chemistry F11, The University of Sydney, NSW 2006, Australia.
Ortin
Yannick
Y
Mueller-Bunz
Helge
H
Rutledge
Peter J
PJ
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