Computational insights into the origins of regio- and enantioselectivities in palladium-catalyzed allylic substitution reactions

Abstract

Pd-catalyzed allylic substitution reactions represent one of the most important and straightforward protocols for the construction of C–C and C–X bonds. In recent years, significant progress has been made in theoretical studies of these reactions, including proposals of the inner-sphere and outer-sphere nucleophilic attack transition state models, particularly with further elucidation of the origins of regio- and enantioselectivities, based on these key models which serve as the selectivity-determining step. This review focus on elucidating the origins of regio- and enantioselectivities within the framework of selectivity-determining nucleophilic attack transition state models, based on density functional theory calculations. The origins of the selectivities are intricate and diverse, inherently linked to the nature of the ligands and the substrates involved in the reactions. Herein, we highlight representative advancements in theoretical studies, aiming to provide crucial mechanistic insights into transition state models and the origins of the regio- and enantioselectivities.

Graphical abstract: Computational insights into the origins of regio- and enantioselectivities in palladium-catalyzed allylic substitution reactions

Article information

Article type
Review Article
Submitted
30 Apr 2025
Accepted
14 Jul 2025
First published
14 Jul 2025

Org. Biomol. Chem., 2025, Advance Article

Computational insights into the origins of regio- and enantioselectivities in palladium-catalyzed allylic substitution reactions

H. Wu, D. Pan, X. Yan and G. Huang, Org. Biomol. Chem., 2025, Advance Article , DOI: 10.1039/D5OB00707K

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