Oxidizing Organic Cyanides

See allHide authors and affiliations

Science  28 Oct 2005:
Vol. 310, Issue 5748, pp. 593
DOI: 10.1126/science.310.5748.593c

Copper monooxygenases can use O2 to hydroxylate a wide variety of substrates; for example, dopamine α-monooxygenase can convert benzylcyanide to benzaldehyde and cyanide. Li et al. have synthesized a dicopper complex that can hydroxylate nitriles. A binucleating ligand was used that binds two Cu(I) ions through three N atoms and thus allows each Cu(I) to also coordinate a nitrile; an OH on the bridging portion of the ligand is noncoordinating. Addition of O2 at -80°C in nitrile solvent produced a hydroperoxide-bridged Cu(II) species in which the alkylamino N atoms no longer bind the Cu atoms. Warming to room temperature forms the aldehyde from one solvent nitrile, apparently by first eliminating water to form an α-hydroxynitrile that rearranges to leave one Cu(II) with a cyanide ligand. This species then dimerizes to form a tetranuclear Cu(II) complex. — PDS

J. Am. Chem. Soc. 10.1021/ja054948a (2005).

Navigate This Article