Transition Metal‐Promoted Direct CS and CSe Bond Formation from Csp³H Bonds

The transition metal‐catalyzed direct CS and CSe bond formation from CH 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. CY bonds (YS, 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 CS and CSe 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 CS and CSe bonds in the last decade is provided, looking to motivate the continuous discovery of innovative and efficient systems for these transformations.