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Nickel Catalysis: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Nickel catalysis, within catalytic cross-coupling chemistry, is the use of nickel complexes to mediate carbon–carbon and carbon–heteroatom bond construction through organonickel intermediates that cycle among accessible oxidation states, commonly Ni(0)/Ni(II) and Ni(I)/Ni(III) [1]. The concept is bounded by elementary steps of oxidative addition, transmetalation or radical capture, and reductive elimination at a nickel center, and it excludes processes in which nickel functions only as a stoichiometric reductant. Essential features include the earth-abundant metal’s comparatively high electropositivity, its ready access to one-electron pathways, and its capacity to activate bonds that are reluctant toward palladium, including certain C–O, C–N, and C–Cl linkages [1][2]. Dual catalytic manifolds merge a photoredox cycle with a nickel cycle so that an alkyl radical is captured by nickel and then coupled with an aryl electrophile [2][3]. Nickel also promotes the Nozaki–Hiyama–Kishi addition of alkenylchromium reagents generated from alkenyl triflates [4]. The field is distinguished from palladium catalysis by the greater incidence of radical elementary steps and by a different functional-group activation profile.

  • nickel catalysis
  • cross-coupling
  • organonickel intermediate
  • dual catalysis

Catalytic Cross-Coupling Reactions • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Sarah Z. Tasker; Eric A. Standley; Timothy F. Jamison; Recent advances in homogeneous nickel catalysis. Nature 2014, 509, 299-309, 10.1038/nature13274.
  2. Zhiwei Zuo; Derek T. Ahneman; Lingling Chu; Jack A. Terrett; Abigail G. Doyle; David W. C. MacMillan; Merging photoredox with nickel catalysis: Coupling of α-carboxyl sp 3 -carbons with aryl halides. Science 2014, 345, 437-440, 10.1126/science.1255525.
  3. Zhiwei Zuo; Huan Cong; Wei Li; Junwon Choi; Gregory C. Fu; David W. C. MacMillan; Enantioselective Decarboxylative Arylation of α-Amino Acids via the Merger of Photoredox and Nickel Catalysis. J. Am. Chem. Soc. 2016, 138, 1832-1835, 10.1021/jacs.5b13211.
  4. K. Takai; M. Tagashira; T. Kuroda; K. Oshima; K. Utimoto; H. Nozaki; Reactions of alkenylchromium reagents prepared from alkenyl trifluoromethanesulfonates (triflates) with chromium(II) chloride under nickel catalysis. J. Am. Chem. Soc. 1986, 108, 6048-6050, 10.1021/ja00279a068.
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