An efficient arylation/C−C activation process was discovered by Prof. LEI Aiwen, visiting professor of the State Key Laboratory for Oxo Synthesis and Selective Oxidation. β-Diketones and aryl halides (aryl iodides and aryl bromides) could undergo reaction smoothly in the presence of Cu(I) or Cu(II) salts in DMSO using K3PO4·3H2O without ligands. The role of H2O was unprecedented, which assisted the C-C activation. Various R-aryl ketones could be efficiently synthesized from this novel method. In situ monitoring of the formation of KOAc and experimentation relating to “a classic diagnostic technique for the participation of radical anion intermediates” revealed the preliminary mechanistic information for the reaction.
Transition-metal-catalyzed selective C-C bond activation (cleavage) currently fascinates organometallic chemists, due to not only its fundamental scientific interest but also its potential usage in organic synthesis. Because of the inertness of C-C bonds, only a few examples of the catalytic activation of C-C bonds have been reported before 2000. In recent years, significant progress has been achieved, which involved some effective strategies to activate the C-C bonds.
The R-aryl carbonyl compounds are important components of many pharmaceuticals and bioactive molecules. Because of the economic attractiveness and good functional group tolerance, copper catalysts are remarkably advantageous in chemical syntheses. To the best of the researchers’ knowledge, no examples have been described in literature of R-aryl ketones being prepared using a copper catalyst from the direct arylation of simple ketones.
This method is simple, general, and practical which complemented the classic method for the rapid construction of C-C bonds to a carbonyl moiety. The detailed mechanism is currently under investigation in the laboratory and will be reported in due course.
The work was published in J. AM. CHEM. SOC. (J. AM. CHEM. SOC. 2010, 132, 8273–8275).
Abstract of the paper published in J. AM. CHEM. SOC.
Introduction
