Structurally Modified Norbornenes: A Key Factor to Modulate Reaction Selectivity in the Palladium/Norbornene Cooperative Catalysis

Palladium/norbornene (Pd/NBE) cooperative catalysis has received enormous attention and found numerous synthetic applications in the past two decades. Considering the critical roles that NBE plays in the catalytic cycle, the use of structurally modified NBEs (smNBEs), starting from 2015, has become an important approach to address limitations and modulate reaction selectivity in Pd/NBE catalysis. This Perspective highlights the development of three types of smNBEs: C1-substituted, C2-substituted, and C5-substituted or C5,C6-disubstituted NBEs, as well as their synthetic applications toward site-selective C–H functionalization. A focus is on the structure–activity relationship of smNBEs in these reactions, and rationales for using smNBEs in many cases have also been provided.