Mechanistic study of asymmetric oxidative biaryl coupling: evidence for self-processing of the copper catalyst to achieve control of oxidase vs oxygenase activity.
Copper(I) and copper(II) 1,5-diaza-cis-decalin complexes [(N2)Cu] are effective precatalysts for aerobic oxidative coupling of naphthol substrates. Mechanistic studies, however, reveal that these complexes are not the reactive form of the catalyst under steady-state conditions. Rather, the active catalyst forms in a presteady-state self-processing step that involves oxygenation of the naphthol substrate. The oxygenated substrate, NapHOX, serves as a cofactor that combines with the (N2)Cu complexes to achieve highly selective, steady-state oxidase reactivity (aerobic oxidative biaryl coupling).
Hewgley
J Brian
JB
Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
Stahl
Shannon S
SS
Kozlowski
Marisa C
MC
D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006574:Heterocyclic Compounds, 2-Ring / Q000737:chemistry; D007700:Kinetics; D009284:Naphthols / Q000138:chemical synthesis* / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry* / Q000378:metabolism; D010105:Oxygenases / Q000737:chemistry* / Q000378:metabolism; D010880:Piperidines / Q000737:chemistry
C430116:1,5-diazadecalin; D006574:Heterocyclic Compounds, 2-Ring; D009284:Naphthols; D009942:Organometallic Compounds; D010880:Piperidines; D003300:Copper; D010088:Oxidoreductases; D010105:Oxygenases