Non‐Bonding Interactions Enable the Selective Formation of Branched Products in Palladium‐Catalyzed Allylic Substitution Reactions

Abstract Palladium‐catalyzed allylic substitution reactions have become established as an important tool for the construction of carbon−carbon and carbon−heteroatom bonds in modern organic synthesis. However, controlling the regioselectivity of this type of transformation to afford chiral branched products, in addition to controlling the enantioselectivity, is a significant challenge. Excitingly, controlling nonbonding interactions between the substituents on the π‐allyl−palladium intermediate and the nucleophile or palladium catalyst has been shown to be effective in achieving this goal. This Focus Review highlights representative advances in this field, according to the mode of non‐bonding interaction, including hydrogen‐bonding, electrostatic, and coordination interactions.