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 C-H functionalization, which we view as a promising future direction in the field.
Department of Chemistry, The Scripps Research Institute, 10550 N Torrey Pines Road, La Jolla, CA 92037, USA.
Keary M
KM
Engle
Tian-Sheng
TS
Mei
Xisheng
X
Wang
Jin-Quan
JQ
Yu
D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D005461:Fluorine / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*
D016877:Oxidants; D005461:Fluorine; D010165:Palladium; D002244:Carbon; D006046:Gold
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