Oxidations of C−H and O−H Bonds by Isolated Copper(III) Complexes

Abstract

In oxidations by copper enzymes, copper(III) species are increasingly being proposed as intermediates. A good model for such reactions is the oxidation of dihydroanthracene to anthracene by an isolated copper(III) imine/oxime complex [Eq. (1)].

Pentadentate thioether-oxime macrocyclic and quasi-macrocyclic complexes of copper(II) and nickel(II)

“…Since that time, several N 4 and N 2 S 2 quasi-macrocyclic and BF 2 -macrocyclized oximes have been synthesized [3 -7]. Recently a copper -oxime complex was used to oxidize anthracene [8], while metal-containing oxime complexes are utilized in medicine as well; technetium(V)-and copper(II)-containing 6ic-oximes currently are used as cerebral and myocardial perfusion imaging agents [9][10][11][12][13][14]. This area was also recently reviewed [15,16].…”

The dipeptide H-Aib-l-Ala-OH ligand in copper(II) chemistry: Variation of product identity as a function of pH

“…In the coordination chemistry of Aib-based tripeptides, the X-ray crystal structure of the remarkable copper(III) complex [Cu III (H À2 Aib 3 )] AE 2H 2 O AE 1.5NaClO 4 , containing the trianion of tri-a-amino-isobutyric acid as ligand, had been determined [8]. Reduction of this complex by 2,4-di-tert-butylphenol gave the dinuclear complex [Cu 2 (H À1 Aib 3 ) 2 ] [9]. In our previous work, the crystal structures of Cu(II) complexes with the dianionic forms of dipeptides H-Aib-Aib-OH [10], H-Aib-Gly-OH, HAib-Leu-OH and H-Aib-Phe-OH [11] have been reported.…”

Copper Complexes as Functional Models for Dopamine β-Hydroxylase - Mechanistic Study of Oxygen Atom Transfer from Cu/O Species to Benzylic C−H Bonds

“…Few examples of oxygen atom transfer from a copper center to an exogenous substrate are known. [19,20] To achieve this, the substrate association in the copper coordination sphere still remains to be solved. [21] We think this will be an exciting challenge for the organic chemist.…”