Pd(OAc)2/M(NO3)n (M = Cu(II), Fe(III); n = 2, 3): Kinetic investigations of an alternative Wacker system for the oxidation of natural olefins

Pd-catalyzed oxidative coupling of camphene by dioxygen afforded mainly a diene, which subsequently underwent oxidation to a ring-expanded β,γ-unsaturated ketone with LiNO3 as reoxidant. However, the instability of LiNO3 results to the decomposition of NO3− ions which subsequently deactivates the catalyst. The present investigation describes the oxidation of terpenes catalyzed by Pd(OAc)2/M(NO3)n (M = Cu(II), Fe(III); n = 2 or 3), using dioxygen as final oxidant. Fe(III) and Cu(II) effectively stabilize the nitrate reoxidant as determined by the significant increase of both catalytic activity and stability of the system. Turnover frequency suggests that Fe(III) is the most efficient co-catalyst. Moreover, it is established that the co-catalysts NO3−, Cu(II) and especially Fe(III) ions, change the product distribution (diene/ketone) remarkably. Their involvement in the rate-determining step was investigated and the results of the kinetic investigations clarified important aspects of Pd(II)-catalyzed oxidation reactions. The described protocol offers an alternative to the traditional Wacker system which uses CuCl2 as co-catalyst and is not effective in promoting the oxidation of bicycle olefins.

Graphical abstractThe efficiency of an alternative Wacker system, based on catalytic combination of Pd(OAc)2/Fe(NO3)3 or Pd(OAc)2/Cu(NO3)2, on the oxidation of natural olefins was evaluated. The results of the kinetic investigations regarding the role of palladium catalyst, nitrate ion, dioxygen, and co-catalysts (iron and copper) are discussed.Figure optionsDownload full-size imageDownload as PowerPoint slide