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

Authors


  • 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.

Abstract

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.

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