Catalysis

Electrophile

Palladium

Isoprene

Stereochemistry

Polymer

Combinatorial chemistry

Organic chemistry

Hydroamination

Nucleophile

Copolymer

Regioselectivity

Chemistry

Angewandte Chemie International Edition

Depending on the reactant property and reaction mechanism, one major regioisomer can be favored in a reaction that involves multiple active sites. Herein, an orthogonal regulation of nucleophilic and electrophilic sites in the regiodivergent hydroamination of isoprene with indazoles is demonstrated. Under Pd‐hydride catalysis, the 1,2‐ or 4,3‐insertion pathway with respect to the electrophilic sites on isoprene could be controlled by the choice of ligands. In terms of the nucleophilic sites on indazoles, the reaction occurs at either the N 1 ‐ or N 2 ‐position of indazoles is governed by the acid co‐catalysts. Preliminary experimental studies have been performed to rationalize the mechanism and regioselectivity. This study not only contributes a practical tool for selective functionalization of isoprene, but also provides a guide to manipulate the regioselectivity for the N ‐functionalization of indazoles.

Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene