Alkyl Carbon−Nitrogen Reductive Elimination from Platinum(IV)−Sulfonamide Complexes

Pawlikowski, Andrew V.; Getty, and April D.; Goldberg, Karen I.

doi:10.1021/ja069191h

Cited by 102 publications

(85 citation statements)

References 79 publications

(67 reference statements)

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“…Instead, the dominant electronic effect on reductive elimination seems to result from differences in the electronegativity of the atom bound to the metal58. Apparently, the more covalent and less ionic the M–heteroatom bond, and the more polarizable the heteroatom, the faster the rate of concerted reductive elimination from the intermediates in the catalytic coupling to form C–heteroatom bonds59,60.…”

Section: Catalysis By Carbon–heteroatom Reductive Eliminationmentioning

confidence: 99%

“…Reductive eliminations of alkyl aryl ethers, alkyl acetates and N -alkyl sulphonamides from platinum(IV) that are part of the mechanism of alkane functionalizations (discussed in the next section) occur by a non-concerted mechanism, and these reactions occur faster from complexes containing ligands that can better support anionic charge at the heteroatom than from those whose ligands are less able to support such charge59,60. Reductive elimination from arylpalladium(IV) complexes has also been observed, but it is too soon to draw conclusions about the electronic effects on these reductive eliminations61.…”

Section: Catalysis By Carbon–heteroatom Reductive Eliminationmentioning

confidence: 99%

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Carbon–heteroatom bond formation catalysed by organometallic complexes

Hartwig

2008

Nature

892

351

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At one time the synthetic chemist's last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal-heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future.Organometallic complexes contain organic groups attached to a central metal through metalcarbon (M-C) bonds. These complexes undergo a set of elementary reactions, many of which release products containing new C-C or C-H bonds. The linking of these reactions to generate catalytic processes that form C-C bonds has been a recent focus of synthetic chemistry research. Such organometallic catalysts are now used to form C-C bonds in commodity chemicals (cheap chemicals sold in bulk) and polymers that are produced on the scale of millions of tonnes per year. They are also used in tailor-made polymers that are produced in small quantities and in highly intricate pharmaceuticals and biologically active natural products (see page 323), which are typically produced in milligram quantities for biological testing.The backbone of many organic compounds is composed of C-C bonds, but the function of these molecules is often derived from the presence of heteroatoms, such as nitrogen, oxygen and sulphur, which are held in these molecules by C-heteroatom bonds. For example, pharmaceuticals and conductive polymers (plastics that conduct electricity) often contain amine C-N bonds, and almost all natural products contain ether, ketone or ester C-O bonds. Heterocyclic compounds in which C-N, C-O or C-S bonds are present in the ring structure are found in all applications of chemistry. Moreover, useful intermediates in synthesis often contain C-B or C-Si bonds that are later converted into C-C, C-O or C-N bonds in the final products.Amines, alkoxides, thiolates and related reagents are common nucleophiles in reactions that occur without a catalyst. However, these reagents do not react with the weak electrophiles that are useful for synthesis, such as aromatic halides, and they do not react with common electronrich reagents, such as alkenes. Thus, the ability to carry out catalytic reactions that form these Correspondence should be addressed to the author (jhartwig@uiuc.edu). Author Information Reprints and permissions information is available at www.nature.com/reprints. The author declares no competing financial interests. NIH Public Access Author ManuscriptNature. Author man...

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Section: Catalysis By Carbon–heteroatom Reductive Eliminationmentioning

confidence: 99%

Section: Catalysis By Carbon–heteroatom Reductive Eliminationmentioning

confidence: 99%

Carbon–heteroatom bond formation catalysed by organometallic complexes

Hartwig

2008

Nature

892

351

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“…Products derived from competing C(sp 2 )-C(sp 3 ) coupling or C(sp 2 )-heteroatom coupling were not detected in the 1 H NMR spectra of the crude reaction mixtures. Notably, C(sp 3 )-heteroatom coupling reactions of this type are rare in organometallic chemistry (20)(21)(22)(30)(31)(32)(33)(34), and most previously reported examples involve second or third row metal centers. In addition, the observation of selective C(sp 3 )-heteroatom coupling is complementary to the reactivity of other oxidation states of Ni, where C(sp 2 )-heteroatom bond-formation has significant precedent (35)(36)(37).…”

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confidence: 99%

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

Camasso

Sanford

2015

Science

267

182

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Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni(0), Ni(I), Ni(II), and/or Ni(III) oxidation states. In contrast, Ni(IV) intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic Ni(IV) complexes, accessed by the reaction of Ni(II) precursors with the widely used oxidant S-(trifluoromethyl)dibenzothiophenium triflate. These Ni(IV) complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, and carbon(sp(3))-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-heteroatom coupling reactions.

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“…Hillhouse has reported the intramolecular reductive elimination of an indoline from a nickel amide in the presence of an oxidant, 2,3 and Goldberg has reported the reductive elimination of a sulfonamide from a methylplatinum(IV) sulfonamido complex by dissociation of the sulfonamide ligand. 4 However, the direct, thermal reductive elimination of an alkylamine from an isolated, low-valent metal amido complex is not well documented. 5 Several palladium-catalyzed reactions have been proposed to occur by reductive elimination from a palladium amido complex to form new C(sp 3 )−N bonds.…”

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confidence: 99%

Reductive Elimination of Alkylamines from Low-Valent, Alkylpalladium(II) Amido Complexes

et al. 2012

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A series of three-coordinate norbornylpalladium amido complexes ligated by bulky N-heterocyclic carbene (NHC) ligands were prepared that undergo reductive eliminations to form the alkyl−nitrogen bond of alkylamine products. The rates of reductive elimination reveal that complexes containing more-electron-donating amido groups react faster than those with less-electrondonating amido groups, and complexes containing moresterically bulky amido groups undergo reductive elimination more slowly than complexes containing lesssterically bulky amido groups. Complexes ligated by more-electron-donating ancillary NHC ligands undergo reductive elimination faster than complexes ligated by lesselectron-donating NHC ligands. In contrast to the reductive elimination of benzylamines from bisphosphine-ligated palladium amides, these reactions occur with retention of configuration at the alkyl group, indicating that these reductive eliminations proceed by a concerted pathway. The experimentally determined free energy barrier of 26 kcal/mol is close to the computed free energy barrier of 23.9 kcal/mol (363 K) for a concerted reductive elimination from the isolated, three-coordinate NHC-ligated palladium anilido complex.

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Alkyl Carbon−Nitrogen Reductive Elimination from Platinum(IV)−Sulfonamide Complexes

Cited by 102 publications

References 79 publications

Carbon–heteroatom bond formation catalysed by organometallic complexes

Carbon–heteroatom bond formation catalysed by organometallic complexes

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

Reductive Elimination of Alkylamines from Low-Valent, Alkylpalladium(II) Amido Complexes

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