Bystanding F + Oxidants Enable Selective Reductive Elimination from High‐Valent Metal Centers in Catalysis

Reductive elimination from partially or completely oxidized metal centers is a vital step in a myriad of carbon–carbon and carbon–heteroatom bond‐forming reactions. One strategy for promoting otherwise challenging reductive elimination reactions is to oxidize the metal center using a two‐electron oxidant (that is, from M (n) to M (n+2) ). However, many of the commonly used oxidants for this type of transformation contain oxygen, nitrogen, or halogen moieties that are subsequently capable of participating in reductive elimination, thus leading to a mixture of products. In this Minireview, we examine the use of bystanding F + oxidants for addressing this widespread problem in organometallic chemistry and describe recent applications in Pd II /Pd IV and Au I /Au III catalysis. We then briefly discuss a rare example in which one‐electron oxidants have been shown to promote selective reductive elimination in palladium(II)‐catalyzed CH functionalization, which we view as a promising future direction in the field.