Substituent-Induced Hyperconjugation: Origin of the Structural Effects on the Efficiency of Photochemical Ring Opening.

ABSTRACT

Photochemical ring-opening reactions are among the most extensively employed chemical reactions in the field of chemistry. Owing to their significance, molecular-level studies of these reactions have been widely conducted. One of the major considerations in investigating the ring-opening dynamics of complex molecules on the molecular scale is the differences in dynamics between different conformers because the number of conformers arising from a specific substrate rapidly increases with the complexity of the substrate. However, to date, studies dealing with this problem have been limited to specific individual cases. That is, a rule applicable to arbitrary conformers to estimate and explain the effects of the molecular structure, such as substituents and conformations, on photochemical ring opening has not been established. Herein, we propose the concept of substituent-induced electron density leakage via hyperconjugation as a candidate for this general rule. Based on our hypothesis, we present an indicator that can predict the efficiency of the photochemical ring-opening reactions of various conformers. The relative error between the ring-opening efficiency as obtained from the indicator and that obtained from the nonadiabatic simulations was less than 25% in 56 of the 66 conformers arising from 1,3-cyclohexadiene and 12 distinct analogues. This approach offers the possibility of accurately and quickly predicting the photochemical ring-opening efficiency of arbitrary molecules in arbitrary conformations.