Mechanistic study of asymmetric oxidative biaryl coupling: evidence for self-processing of the copper catalyst to achieve control of oxidase vs oxygenase activity.

J Brian Hewgley, Shannon S Stahl, Marisa C Kozlowski

Journal of the American Chemical Society 2008 Sep 17

filter terms:

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).

Citation

J Brian Hewgley, Shannon S Stahl, Marisa C Kozlowski. Mechanistic study of asymmetric oxidative biaryl coupling: evidence for self-processing of the copper catalyst to achieve control of oxidase vs oxygenase activity. Journal of the American Chemical Society. 2008 Sep 17;130(37):12232-3