Chirality of the Conformation Attacks the Planarity of the sp² Carbon Atom in a Covalent Bond

The correlation of the rotation about the bond C′–C_α and the pyramidalization of the sp² hybridized carbon atom C′ and its three bonding partners to a flattened tetrahedron was investigated for the substructure C_β–C_αH–C′(O)–OMe. A search in the Cambridge Structural Database (CSD) gave 15,295 structures with a substituted methyl acetate group at the end of the molecules. The scatter plot of the rotation angle ψ = OC′–C_α–C_β versus the pyramidalization angle θ = O­(MeO)­C′C_α and the ψ/θ_av curve show an unusual undulating pattern with three maxima and minima for a 360° rotation about the bond C′–C_α. There is no net chiral induction from the (M_ψ)/(P_ψ) conformations of the bond C′–C_α to the (R_θ)/(S_θ) configurations of the flattened tetrahedron because the contributions of the three maxima and minima cancel each other. The wavelike ψ/θ_av curve demonstrates that the rotation about the bond C′–C_α and the pyramidalization of the group C′(O)­(OMe)­C_α are not independent processes. They are coupled with each other in one common molecular motion. The ψ/θ_av curve appears as the third harmonic of a sinusoidal fundamental frequency. DFT calculations of the propanoate anion, methyl propanoate, and methyl 2-methylpropanoate confirm the results of the CSD search.