C-S bond formation reaction between a phenolate and disulfide-bridged dicopper(I) complexes.
A novel C-S bond formation reaction took place, when a lithium phenolate derivative was treated with a disulfide-bridged dicopper(I) complex or a bis(micro-thiolato)dicopper(II) complex under very mild conditions. The reaction has been suggested to proceed via a disulfide-bridged (micro-phenoxo)dicopper(I) complex as the common reaction intermediate. Copper(II) complexes of the modified ligands containing a thioether group (products of the C-S bond formation reaction) have been isolated and structurally characterized by X-ray analysis as model compounds of the active site of galactose oxidase. Mechanism of the C-S bond formation reaction is also discussed in relation to the biosynthetic mechanism of the organic cofactor Tyr-Cys of galactose oxidase.
Osako
Takao
T
Department of Chemistry, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
Ueno
Yoshiki
Y
Tachi
Yoshimitsu
Y
Itoh
Shinobu
S
D001665:Binding Sites; D001952:Bridged-Ring Compounds / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003553:Cystine / Q000737:chemistry; D004220:Disulfides / Q000737:chemistry*; D005692:Galactose Oxidase / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D014443:Tyrosine / Q000737:chemistry
D001952:Bridged-Ring Compounds; D004220:Disulfides; D009942:Organometallic Compounds; D014443:Tyrosine; D003553:Cystine; D003300:Copper; D005692:Galactose Oxidase