Nickel‐Catalyzed Cross‐Coupling Reactions

Adhikary, Anubendu; Guan, Huashi

doi:10.1002/9783527681303.ch5

Cited by 11 publications

(3 citation statements)

References 94 publications

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“…One of the well-explored catalytic applications of pincer complexes is for cross-coupling reactions . Palladium complex 20 and its derivatives, reported in 2000 by the research groups of Jensen and Bedford, are actually the very first known POCOP-pincer complexes.…”

Section: Discrete Metallacyclesmentioning

confidence: 99%

Catalysis Involving Phosphinite-Based Metallacycles

Adhikary

Guan

2015

ACS Catal.

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Phosphinite-based metallacycles are important intermediates, catalyst precursors, or catalysts for a variety of chemical transformations. Facile, reversible formation of P−O bonds allows phosphinites to act as catalytic directing groups that lead to more efficient and selective metal-catalyzed processes. Relatively low costs and convenient syntheses make metallacyclic phosphinite complexes attractive compounds for catalytic studies. Given the high interest in developing the related phosphine-and phosphite-based catalysts, this Perspective focuses specifically on the comparisons between these different metallacyclic complexes in catalytic reactions. In a number of examples, phosphinite-based metallacycles are more efficient catalysts due to better-matched ligand properties for rate-limiting steps or faster conversion of the complexes to catalytically active species.

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Section: Discrete Metallacyclesmentioning

confidence: 99%

Catalysis Involving Phosphinite-Based Metallacycles

Adhikary

Guan

2015

ACS Catal.

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“…We have previously demonstrated that such Ni complexes are efficient precatalysts for a variety of Kumada-type C–C cross-coupling reactions under mild conditions . Moreover, examples of catalytic C–X cross-coupling reactions with Ni pincer complexes where X = N, O, or S are quite rare, with the best-studied examples involving formation of C–S bonds. − Guan has reported elegant mechanistic work concerning C–S cross-coupling reactions catalyzed by Ni pincer complexes containing the bis (phosphinite) POCOP ligand. , These studies delineated the thermodynamic role of pincer ligand substituent and thiol in stoichiometric C–S bond forming steps and demonstrated that lower valent Ni complexes resulting from decomposition of the pincer ligand are likely the true catalytically active species. Zargarian has also studied such ligand decomposition pathways in detail for related POCOP pincers containing a central C sp 3 donor atom .…”

Section: Introductionmentioning

confidence: 99%

Catalytic C–S Cross-Coupling Reactions Employing Ni Complexes of Pyrrole-Based Pincer Ligands

2014

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A series of catalytic C–S coupling reactions utilizing well-defined Ni(II) PNP pincer complexes as precatalysts are reported (PNP = anion of 2,5-bis[(dialkyl/aryl-phosphino)methyl]pyrrole, abbreviated as P2 RPyr). Coupling reactions employing a variety of aryl iodides and thiols in the presence of base and DMF proceed in good to excellent yield at 80 °C with low catalyst loadings. Aryl bromides were found to result in substantially lower yields, and aryl chlorides were found to be unreactive under the catalytic conditions. In an effort to further understand the reactivity of the nickel PNP precatalysts, complexes of Ni(II) containing amide, alkoxide, hydroxide, thiolate, and hydrosulfide ligands have been prepared and examined in stoichiometric reactions relevant to carbon-heteroatom coupling. Full characterization of each nickel complex is provided, including solid-state structures. The results of stoichiometric reactions implicate a reduced Ni(I) species as the active catalyst, which forms by reduction of the Ni(II) precatalyst in the presence of excess thiolate. The facility in forming Ni(I) species is invoked to rationalize the observed activity among different Ni PNP precatalysts.

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“…Other Pd-based catalysts were active, but the yields were consistently lower than that with the Pd(P- t -Bu 3 ) 2 system (entries 3–5). Ni-based precatalysts gave poor yields and complex reaction mixtures (entries 6 and 7). , A solvent switch to diethyl ether (entry 8) was not detrimental to the observed yield of 3a . However, the use of a nonpolar solvent such as toluene decreased the yield of 3a significantly (entry 9).…”

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confidence: 98%

Negishi Cross-Coupling Is Compatible with a Reactive B–Cl Bond: Development of a Versatile Late-Stage Functionalization of 1,2-Azaborines and Its Application to the Synthesis of New BN Isosteres of Naphthalene and Indenyl

Brown

Liu

2015

J. Am. Chem. Soc.

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The compatibility of the Negishi cross-coupling reaction with the versatile B–Cl functionality has been demonstrated in the context of late-stage functionalization of 1,2-azaborines. Alkyl-, aryl-, and alkenylzinc reagents have been utilized for the functionalization of the triply orthogonal precursor 3-bromo-1-(tert-butyldimethylsilyl)-2-chloro-1,2-dihydro-1,2-azaborine (2) to furnish new 2,3-substituted monocyclic 1,2-azaborines. This methodology has enabled the synthesis of previously elusive BN-naphthalene and BN-indenyl structures from a common intermediate.

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Nickel‐Catalyzed Cross‐Coupling Reactions

Cited by 11 publications

References 94 publications

Catalysis Involving Phosphinite-Based Metallacycles

Catalysis Involving Phosphinite-Based Metallacycles

Catalytic C–S Cross-Coupling Reactions Employing Ni Complexes of Pyrrole-Based Pincer Ligands

Negishi Cross-Coupling Is Compatible with a Reactive B–Cl Bond: Development of a Versatile Late-Stage Functionalization of 1,2-Azaborines and Its Application to the Synthesis of New BN Isosteres of Naphthalene and Indenyl

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