Multitechnique Approach to Reveal the Mechanism of Copper(II)-Catalyzed Arylation Reactions

作者：Tromp Moniek^*; van Strijdonck Gino P F; van Berkel Sander S; van den Hoogenband Adri; Feiters Martinus C; de Bruin Bas; Fiddy Steven G; van der Eerden Ad M J; van Bokhoven Jeroen A; van Leeuwen Piet W N M; Koning**erger Diederik C

来源：Organometallics, 2010, 29(14): 3085-3097.

DOI：10.1021/om9010643

Multiple in situ and time-resolved spectroscopic techniques (EDXAFS, UV-vis, EPR, and NMR), with a focus on simultaneously acquired EDXAFS and time-resolved UV-vis, are described to reveal detailed structural and electronic information on reaction intermediates or an important Cu(II)-catalyzed N-arylation of imidazole. The N-arylation of imidazole was performed in it NMP/H(2)O solvent mixture, at ambient temperature and atmosphere, using the commercially available Cu catalyst [Cu(OH)(TMEDA)](2)Cl(2) (I). The spectroscopic study resulted in the characterization of most reaction intermediates, and a novel mechanism for the Cu(II)-catalyzed arylation reaction is proposed. The first and selectivity-determining step is the reaction of the dimeric Cu(II) starting complex with imidazole, forming a mononuclear Cu(II)(imidazole) intermediate, II. After subsequent addition of phenylboronic acid, we propose the formation fa Cu(III)(imidazolate)(phenyl) intermediate, III, which after reductive elimination forms the phenylimidazole product, and a known Cu(I) monomeric species. IV, is identified. Finally, this Cu species is reoxidized, forming back an equilibrium mixture of Cu(II) mononuclear and dinuclear complexes. Inhibition of the reaction by imidazole and phenylimidazole is observed. The phenylboronic acid is, in combination with involved in the oxidation and reoxidation steps in the described catalytic cycle.

• 出版日期2010-7-26