Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes

@article{Camasso2015DesignSA,
  title={Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes},
  author={Nicole M. Camasso and Melanie S. Sanford},
  journal={Science},
  year={2015},
  volume={347},
  pages={1218 - 1220}
}
Taking advantage of four for a nickel Metal atoms change their oxidation state—i.e., lose or gain electrons—relatively easily. This is a major reason why metal compounds accelerate so many chemical reactions. Camasso and Sanford now report a straightforward way to prepare complexes of nickel in the +4 oxidation state, based on careful tuning of the coordination environment around the metal center (see the Perspective by Riordan). These complexes could prove useful in coupling carbon to oxygen… 
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References

SHOWING 1-10 OF 41 REFERENCES
Organometallic nickel(III) complexes relevant to cross-coupling and carbon-heteroatom bond formation reactions.
TLDR
Overall, these results provide strong evidence for the direct involvement of organometallic Ni(III) species in cross-coupling reactions and oxidatively induced C-heteroatom bond formation reactions.
Palladium-catalyzed ligand-directed C-H functionalization reactions.
TLDR
This is the first comprehensive review encompassing the large body of work in this field over the past 5 years, and will focus specifically on ligand-directed C–H functionalization reactions catalyzed by palladium.
Emergence of palladium(IV) chemistry in synthesis and catalysis.
TLDR
The need to comprehensively review catalytic PdIV chemistry, particularly in organic synthesis, was identified, which draws on aspects from both inorganic (organometallic) and organic chemistry fields, and the historical background to organopalladium(IV) chemistry is detailed.
Cross-coupling reaction of alkyl halides with grignard reagents catalyzed by Ni, Pd, or Cu complexes with pi-carbon ligand(s).
TLDR
New catalytic systems that do not involve M(0) species but proceed via an anionic complex as the key intermediate are developed, and new catalytic reactions use pi-carbon ligands such as pi-allyl units or alkynes instead of heteroatom ligand such as phosphines or amines are extended.
A five-coordinate nickel(II) fluoroalkyl complex as a precursor to a spectroscopically detectable Ni(III) species.
TLDR
It is shown that five-coordinate Ni(II) complexes containing nickel-carbon bonds can readily be prepared given the appropriate precursor, and evidence for the formation of Ni(III) species upon chemical and electrochemical oxidation of the five- coordinate complexes is presented.
Nickel-catalyzed carbon-carbon bond-forming reactions of unactivated tertiary alkyl halides: Suzuki arylations.
TLDR
This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction.
A stable tetraalkyl complex of nickel(IV).
TLDR
It is shown herein that the strained alkene 1 allows us to create and crystallographically study the first tetraalkyl complex of nickel(IV), a mixture of two enantiomers defined by the helicity arising from the trans double bond in the eight-membered ring.
Nickel-catalyzed direct arylation of C(sp3)-H bonds in aliphatic amides via bidentate-chelation assistance.
The Ni-catalyzed, direct arylation of C(sp(3))-H (methyl and methylene) bonds in aliphatic amides containing an 8-aminoquinoline moiety as a bidentate directing group with aryl halides is described.
High-oxidation-state palladium catalysis: new reactivity for organic synthesis.
TLDR
This type of catalysis by palladium in a higher oxidation state is of significant synthetic potential and has been used to develop a series of new synthetic transformations that cannnot be realized within conventional palladium catalysis.
High-valent organometallic copper and palladium in catalysis
TLDR
Recent advances involving both the fundamental chemistry and the applications of these high-valent metal complexes in numerous synthetically useful catalytic transformations are described.
...
...