Chemoselective Synthesis of 2,2‐Disubstituted Indolin‐3‐Ones via Palladium‐Catalyzed Allylation of 3‐Hydroxyindoles

Given the structural and biological significance of their scaffolds, the synthesis of 2,2‐disubstituted indolin‐3‐ones has garnered considerable attention in recent years. To efficiently construct this valuable skeleton, we herein report two palladium‐catalyzed allylation reactions of 3‐hydroxyindoles. The redox‐neutral allylation of internal alkynes provides direct access to 2‐allyl‐2‐carboxylate‐indolin‐3‐ones under mild conditions, whereas gem ‐difluorocyclopropanes serve as fluoroalkylating agents to introduce fluorine atoms and construct the C2 all‐carbon quaternary center in a single step. Both approaches feature broad substrate scope, excellent functional group tolerance, and scalability. The products undergo diverse downstream transformations, offering rapid access to structurally complex and biologically relevant heterocycles.