Unique solvent effect of water in radical cyclization reaction

The radical cyclization reaction in the aqueous environment by Yorimitsu et al. is revisited using the RISM-SCF-cSED method, a hybrid of quantum chemistry and statistical mechanics theory for molecular liquids. The difference between the barrier height of the forward reaction from the intermediate E-rot, the cyclization step, and that of the backward reaction is crucial to the reaction yield. Considering the effect of hydrogen bonding through the RISM theory, we found that the barrier height for the forward reaction is lower, especially in water. In other words, considering microscopic solvation effects clearly shows the difference between water and DMSO solvents, explaining the remarkable acceleration of the reaction in the aqueous environment.

Automated summary

The radical cyclization reaction in aqueous environment by Yorimitsu et al. was reexamined using the RISM-SCF-cSED method, a hybrid approach combining quantum chemistry and statistical mechanics for molecular liquids. The difference in barrier height between the forward reaction from the intermediate E-rot, the cyclization step, and the backward reaction is crucial for the reaction yield. By considering the effect of hydrogen bonding through the RISM theory, it was found that the barrier height for the forward reaction is lower, particularly in water. In other words, accounting for microscopic solvation effects clearly elucidates the disparity between water and DMSO solvents, explaining the significant acceleration of the reaction in the aqueous environment.