Catalytic cyclopropanation of olefins using copper(I) diphosphinoamines

Catalytic cyclopropanation reactions of olefins with ethyl diazoacetate were carried out using copper(I) diphosphinoamine (PPh2)2N(R) (R = iPr, H, Ph and –CH2–C6H4–CHCH2) complexes at 40 °C in chloroform. High yields of the cyclopropanes were obtained in all cases. The rate of the reaction was influenced by the nuclearity of the complex and the binding mode of the ligand which was either bridging or chelating. Comparison of isostructural complexes shows that the rate follows the order R = iPr > H > Ph, where R is the substituent on the N. However, cyclopropane formation versus dimerization of the carbene, and trans to cis ratios of cyclopropane was similar in all cases. The nearly identical selectivity for different products formed was indicative of a common catalytic intermediate. A labile “copper–olefin” complex which does not involve the phosphine or the counterion is the most likely candidate. The differences in the reaction rates for different complexes are attributed to differences in the concentration of the catalytically active species which are in equilibrium with the catalytically inactive copper–phosphinoamine complex. To test the hypothesis a diphosphinoamine polymer complexed to copper(I) was used as a heterogeneous catalyst. Leaching of copper(I) and deactivation of the catalyst confirmed the proposed mechanism.

Copper(I) diphosphinoamine complexes have been employed for catalytic cyclopropanation of olefins. The substituent on the nitrogen of the ligand influenced the rate of cyclopropanation and the reaction rates were found to be dependent on the copper:phosphine ratio. A tentative mechanism is proposed wherein a metal–olefin complex is a common intermediate responsible for catalytic activity.Figure optionsDownload as PowerPoint slide