Transition Metal‐Promoted Direct CS and CSe Bond Formation from Csp 3 H Bonds

The transition metal‐catalyzed direct CS and CSe bond formation from CH bonds has emerged as an efficient synthetic strategy for constructing previously inaccessible organochalcogen compounds, opening a new gateway to late‐stage functionalization of pharmaceutical‐relevant molecules and organic functional materials. CY bonds (YS, Se, Te) also show outstanding strategic relevance as handles to access other valuable functional groups downstream in a synthetic route. Despite the significant progress, the chemo‐, site‐, and enantioselective CS and CSe bond formation from unactivated Csp 3 H bonds is still challenging owing to its low polarity and inertness. Here, a comprehensive overview of the transition metal‐catalyzed direct conversion of unactivated Csp 3 H to CS and CSe bonds in the last decade is provided, looking to motivate the continuous discovery of innovative and efficient systems for these transformations.