Mechanism of Cobalt-Catalyzed Heterodimerization of Acrylates and 1,3-Dienes. A Potential Role of Cationic Cobalt(I) Intermediates

Coupling reactions of feedstock alkenes are promising, but few of these reactions are practiced industrially. Even though recent advances in the synthetic methodology have led to excellent regio- and enantioselectivies in the dimerization reactions between 1,3-dienes and acrylates, the efficiency as measured by the turnover numbers (TONs) in the catalyst has remained modest. Through a combination of reaction progress kinetic analysis (RPKA) of a prototypical dimerization reaction and characterization of isolated low-valent cobalt catalyst precursors involved, several important details of the mechanism of this reaction have emerged. (i) The prototypical reaction has an induction period that requires at least 2 h of stir time to generate the competent catalyst. (ii) Reduction of a Co(II) complex to a Co(I) complex and subsequent generation of a cationic [Co(I)]+ species are responsible for this delay. (iii) Through RPKA using in situ infrared spectroscopy, same excess experiments reveal inhibition by the product toward the end of the reaction, and no catalyst deactivation is observed as long as the diene is present in the medium. The low TON observed is most likely the result of the inherent instability of the putative cationic Co(I) species that catalyzes the reaction. (iv) Different excess experiments suggest that the reaction is first order in the diene and zero order in the acrylate. (v) Catalyst loading experiments show that the catalyst is first order. The orders in the various regents were further confirmed by variable time normalization analysis. (vi) A mechanism based on oxidative dimerization [via Co(I)/Co(III)-cycle] is proposed. Based on the results of this study, it is possible to increase the TON by a factor of 10 by conducting the reaction at an increased concentration of the starting materials, especially the diene, which seems to stabilize the catalytic species.