A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction

Abstract

The DFT calculations of the simplified model of the asymmetric Suzuki-Miyaura coupling reaction were performed at the M062x/LANL2DZ theory level at first. It was found that enantioselective reactions mediated by the palladium complexes of chiral C,P-ligands follow a four-stage mechanism similar to that proposed previously as one of the most credible mechanisms. It should be underlined that the presence of substituents in the substrates and the chiral ligand at ortho positions determines the energies of possible diastereoisomeric transition states and intermediates in initial reaction steps. This suggests that, in practice, a sharp selection of theoretically possible paths of chirality transfer from the catalyst to the product should have a place and, therefore, the absolute configuration of the formed atropisomeric product is defined and can be predicted.

Computationally Assisted Mechanistic Investigation and Development of Pd-Catalyzed Asymmetric Suzuki–Miyaura and Negishi Cross-Coupling Reactions for Tetra-ortho-Substituted Biaryl Synthesis

“…Therefore, all three major steps of the cross-coupling mechanism contribute to the overall selectivity of the reaction (Figure ). Earlier computational studies of the stereoselectivity in Suzuki–Miyaura cross-coupling suggest that oxidative addition is the stereodetermining step . We further develop this idea of early enantioinduction by employing the experimental findings of Denmark, , Hartwig, and others , that point to the mechanism of the transmetalation step proceeding through a Pd–OH complex .…”

“…Earlier computational studies of the stereoselectivity in Suzuki-Miyaura cross-coupling suggest that oxidative addition is the stereodetermining step. 43 We further develop this idea of early enantioinduction by employing the experimental findings of Denmark, 42a,b Hartwig, 42c and others 42d,e that point to the mechanism of the transmetalation step proceeding through a Pd-OH complex. 17 The exact mechanism for the transmetalation step in Suzuki-Miyaura cross-coupling is still somewhat controversial 39 as there are some reports 44 that support the alternate “boronate”-transmetalation pathway.…”

New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

“…The quantum chemical calculation performed at the M062x/LANL2DZ theoretical level [27,28], which is specially dedicated to precise energetic considerations and has recently been applied in the simulation of energetic and structural analyses of molecules with similar structural moieties [29,30,31,32,33], allows us to compare the geometry of the molecules of phosphines 6 , their dioxides and complexes that were not crystallised in crystals, well-measurable by a single crystal X-ray diffraction. The geometry optimisation for the structure [Pd( 6q )Cl 2 ] was therefore performed and the obtained geometry parameters of [Pd( 6q )Cl 2 ] calc were compared with those received from the X-ray diffraction experiments for [Pd( 6q )Cl 2 ] xray .…”

Cluster model DFT study of lactic acid dehydration over Fe and Sn-BEA zeolite

“…41,42 All Kohn-Sham orbitals are represented by linear combinations of atomic orbitals (LCAO's) using extended contracted Gaussian basis sets for the atoms. 43,44 A detailed analysis of the electronic structure of the clusters was carried out using Mulliken populations 45 and Mayer bond order indices 46,47 . The adsorption energies of the adsorbates on the cluster were calculated as follows:…”