A Nickel-Containing Model System of Acireductone Dioxygenases that Utilizes a C(1)-H Acireductone Substrate

作者：Allpress Caleb J; Berreau Lisa M^*

来源：European Journal of Inorganic Chemistry, 2014, 2014(27): 4642-4649.

DOI：10.1002/ejic.201402254

• Enzyme mimics
• Metalloenzymes
• Nickel
• Oxygen
• Cleavage reactions
• Regioselectivity

A mononuclear Ni-II complex bearing the monoanion of 1-acetoxy-3-phenylpropane-2,3-dione (4) as a ligand has been prepared {[(6-Ph(2)TPA)Ni{PhC(O)C(O)CHOC(O)CH3)]ClO4, 5; 6-Ph(2)TPA = N,N-bis[(6-phenyl-2-pyridyl) methyl]-N-(2-pyridylmethyl)amine}. This complex was characterized by H-1 NMR, UV/Vis and IR spectroscopy, mass spectrometry, and elemental analysis. Exposure of solutions of 5 to O-2 did not result in any reaction over the course of hours. Deprotection of 5 by the addition of NaOCH3 in methanol generated a Ni-II species (6) that contains a coordinated dianionic C(1)-H acireductone. Exposure of 6 to O-2 led to regioselective oxidative cleavage reactivity akin to that found for the Ni-II-containing acireductone dioxygenase enzyme. The strategy outlined herein is the first synthetic approach that enables examination of the oxidative reactivity of a synthetic Ni-II species containing a dianionic C(1)-H acireductone ligand.

• 出版日期2014-9