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


  • We gratefully acknowledge TSRI, the NSF (NSF CHE-0615716, the NIH (NIGMS, 1 R01 GM084019-01A1), and Pfizer for financial assistance. Additional support was provided through the NSF Center for Stereoselective C[BOND]H Functionalization (CHE-0943980). Individual awards and fellowships were granted by the NSF, the DOD, and the Skaggs Oxford Scholarship program (K.M.E.); the Chinese Government (T.-S.M.); and the Dreyfus and Sloan Foundations (J.-Q.Y.). This Minireview is written in celebration of Prof. F. D. Toste’s Tetrahedron Young Investigator Award (2011). TSRI Manuscript no. 20877.


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 PdII/PdIV and AuI/AuIII 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 C[BOND]H functionalization, which we view as a promising future direction in the field.