Preparation and DFT studies of chiral Cu (I)-complexes of biphenyl bisoxazolines and their application in enantioselective Kharasch-Sosnovsky reaction.

Effect of a range of t-butyl perbenzoates bearing electron-withdrawing and electron-donating substitutions on the phenyl ring and HZSM-5 as a porous additive at 0 °C in enantioselective allylic C-H bond oxidation of cyclic and acyclic olefins in the presence of Cu (I)-(S,aS,S) complexes of biphenyl bisoxazoline ligands, produced easily through the chelation-induced process, were investigated. The enantioenriched allylic esters were obtained in reasonable times with excellent enantioselectivities and yields using electron-withdrawing substituted peresters in the presence of Cu (I)-(S,aS,S)-1a complex, containing phenyl groups at the stereogenic centers of the oxazoline moieties. To reach a better insight on geometry, chemical activity, enantioselectivity, and thermodynamic stability of the Cu (I)-BOX complexes, DFT calculations with B3LYP-D3/6-31G (d, p) level of theory were applied to them. Moreover, NBO analysis was used to illustrate interactions between orbitals.