π-π stacking assisted regioselectivity regulation in palladium-catalyzed cyclization reactions: a theoretical study.

The regulation of regioselectivity is an objective often pursued by organic chemists, and the comprehension of its mechanisms is crucial for devising efficient synthetic pathways. In this report, we conducted theoretical calculations to explore the regioselectivity regulatory mechanisms of two palladium-catalyzed cyclization reactions. In these cyclization reactions, manipulating the structural differences in the reaction substrates leads to the formation of distinct products. A detailed reaction mechanism and reactivity profile for this reaction were revealed. Furthermore, a π-π stacking assisted regioselectivity regulatory mechanism was proven by distortion-interaction energy analysis and noncovalent interaction calculations. The calculated results presented herein provide a theoretical guide for further experimental investigations of regioselectivity regulation.