Chirality transition in the epoxidation of (−)-α-pinene and successive hydrolysis studied by Raman optical activity and DFT

Abstract

Characterization of the chirality evolution involved in chemical and biochemical reaction processes is extremely important to the understanding of the chiral catalysis mechanism. In this work, the chiral transition from the epoxidation of (−)-α-pinene to α-pinene oxide and successive hydrolysis to (−)-pinanediol has been studied as an archetype of the asymmetric catalysis by Raman optical activity (ROA) and the DFT calculation. Minor changes of the absolute configuration of the chiral products from (−)-α-pinene to (−)-pinanediol lead to the dramatic variation in ROA spectra indicating that the chirality is delocalized in the whole molecule rather than only concentrated on the chiral centers. The oxygen atom of α-pinene oxide contributes strong ROA signals while the two hydroxyl groups of (−)-pinanediol give no apparent contribution to the chirality in terms of ROA signals. Isolation of the two symmetric anisotropic invariants shows that the predominant contribution to the ROA signals stems from the electric dipole–magnetic dipole invariant, and the bond polarizability model is indeed found to be a good approximation for molecules composed of entirely axially-symmetric bonds in α-pinene oxide and (−)-pinanediol. This study demonstrates the feasibility of using ROA to sensitively monitor the variation of the chirality transition during the chiral reactions either in the chemical or biological system.