In Praise of Basic Research as a Vehicle to Practical Applications: Palladium‐Catalyzed Coupling to Form Carbon‐Nitrogen Bonds

Buchwald, Stephen L.; Hartwig, John F.

doi:10.1002/ijch.201900167

Cited by 16 publications

(25 citation statements)

References 39 publications

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“…Regarding C−N coupling reactions, aryl amination via combined photoredox/nickel catalysis is a key discovery that attracted considerable attention (Figure 2 a), [20a] because this represents a complementary method to analogous palladium catalyzed reactions [36] . In particular, the reductive elimination step resulting in C−N bond formation was much in focus.…”

Section: Scope Of Light‐driven Nickel‐catalyzed Cross‐coupling Reactionsmentioning

confidence: 99%

“…Regarding CÀNc oupling reactions, aryl amination via combined photoredox/nickel catalysis is ak ey discoveryt hat attracted considerable attention (Figure 2a), [20a] because thisr epresents ac omplementary method to analogous palladium catalyzed reactions. [36] In particular, the reductive elimination step resultingi nC ÀNb ond formation was much in focus. Partly based on early studies,w hich indicated that Ni II amido complexes tend to not undergo reductiveelimination at room temperature, [17] photo-driven oxidationo fN i II to Ni III wasc onsidered essential.…”

Section: Scope Of Light-driven Nickel-catalyzedc Ross-coupling Reactionsmentioning

confidence: 99%

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Photoactive Nickel Complexes in Cross‐Coupling Catalysis

Wenger

2020

Chemistry A European J

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Transition metal catalyzed cross‐coupling reactions are important in chemical synthesis for the formation of C−C and C‐heteroatom bonds. Suitable catalysts are frequently based on palladium or nickel, and lately the cheaper and more abundant first‐row transition metal element has been much in focus. The combination of nickel catalysis with photoredox chemistry has opened new synthetic possibilities, and in some cases electronically excited states of nickel complexes play a key role. This is a remarkable finding, because photo‐excited metal complexes are underexplored in the context of organic bond‐forming reactions, and because the photophysics and the photochemistry of first‐row transition metal complexes are underdeveloped in comparison with their precious metal‐based congeners. Consequently, there is much potential for innovation at the interface of synthetic‐organic and physical‐inorganic chemistry. This Minireview highlights recent key findings in light‐driven nickel catalysis and identifies essential concepts for the exploitation of photoactive nickel complexes in organic synthesis.

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Section: Scope Of Light‐driven Nickel‐catalyzed Cross‐coupling Reactionsmentioning

confidence: 99%

Section: Scope Of Light-driven Nickel-catalyzedc Ross-coupling Reactionsmentioning

confidence: 99%

Photoactive Nickel Complexes in Cross‐Coupling Catalysis

Wenger

2020

Chemistry A European J

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“…The Buchwald–Hartwig amination − is a chemical reaction used in organic chemistry for the synthesis of carbon–nitrogen bond-containing products. The reaction is a coupling of amines with arylhalides via a palladium catalyst. , This process has simplified the synthesis of pharmaceutical and agrochemical agents, among other relevant chemicals.…”

Section: Introductionmentioning

confidence: 99%

Computational Analysis on the Pd-Catalyzed C–N Coupling of Ammonia with Aryl Bromides Using a Chelate Phosphine Ligand

2021

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The Buchwald–Hartwig amination of arylhalides with the Pd–Josiphos complex is a very useful process for the generation of primary amines using ammonia as a reactant. Density-functional theory (DFT) calculations are carried out to examine the reaction mechanism for this process. Although the general mechanism for the C–N cross-coupling reaction is known, there are still some open questions regarding the effect of a chelate phosphine ligand and the role of the base in the process. Reaction pathways involving the release of one of the arms of the phosphine ligand are compared with those where the chelate phosphine remains fully coordinated. Conformational analysis for the complex with the open chelate phosphine is required to properly evaluate the proposed pathways. The role played by the added base (t-BuO–) as a possible ligand or just as a base was also evaluated. The understanding of all of these aspects allowed us to propose a complete reaction mechanism for the Pd-catalyzed C–N coupling of arylhalides with ammonia using the chelate Josiphos ligand.

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“…Palladium-catalyzed cross-coupling is one of the most powerful tools in modern synthetic chemistry, [1][2][3] with widespread application in total synthesis, 4 pharmaceutical discovery and process chemistry, [5][6][7] agrochemistry, 8 and materials synthesis. 9 Given the large number of reaction variables to optimize for every new system, there is a daunting variety of reported reaction conditions for each general transformation.…”

Section: Introductionmentioning

confidence: 99%

(DMP)DAB–Pd–MAH: A Versatile Pd(0) Source for Precatalyst Formation, Reaction Screening, and Preparative-Scale Synthesis

Huang¹,

Isaac²,

Watt³

et al. 2021

Preprint

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We report an easily prepared and bench-stable mononuclear Pd(0) source stabilized by a chelating N,N’-diaryldiazabutadiene ligand and maleic anhydride: DMPDAB–Pd–MAH. Phosphine ligands of all types, including bidentate phosphines and large cone angle biarylphosphines, rapidly and completely displace the diazabutadiene ligand at room temperature to give air-stable Pd(0) phosphine complexes. DMPDAB–Pd–MAH itself is readily soluble and stable in several organic solvents, making it an ideal Pd source for in situ catalyst preparation during reaction screening, as well as solution-dispensing to plate-based reaction arrays for high-throughput experimentation. Evaluation of DMPDAB–Pd–MAH alongside other common Pd(0) and Pd(II) sources in microscale reaction screens reveals that DMPDAB–Pd–MAH is superior at identifying hits across six different C–N, C–C, and C–O coupling reactions. DMPDAB–Pd–MAH, and the phosphine precatalysts derived therefrom, are also effective in preparative-scale cross couplings at low Pd loadings.

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In Praise of Basic Research as a Vehicle to Practical Applications: Palladium‐Catalyzed Coupling to Form Carbon‐Nitrogen Bonds

Cited by 16 publications

References 39 publications

Photoactive Nickel Complexes in Cross‐Coupling Catalysis

Photoactive Nickel Complexes in Cross‐Coupling Catalysis

Computational Analysis on the Pd-Catalyzed C–N Coupling of Ammonia with Aryl Bromides Using a Chelate Phosphine Ligand

(DMP)DAB–Pd–MAH: A Versatile Pd(0) Source for Precatalyst Formation, Reaction Screening, and Preparative-Scale Synthesis

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