C(sp3)–H Bond Acylation with N-Acyl Imides under Photoredox/ Nickel Dual Catalysis

Kerackian, Taline; Reina, Antonio; Krachko, Tetiana; Boddaert, Hugo; Bouyssi, Didier; Monteiro, Nuno; Amgoune, Abderrahmane

doi:10.1055/s-0040-1707301

Cited by 11 publications

(12 citation statements)

References 10 publications

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“…Instead, 4 may play a role in the prevention of unproductive Ni oligomerization 87,89,94,95 or the formation of off-cycle N-acyl-imide Ni complexes. 89,96 On the basis of literature precedent, 59,97,98 mechanistic studies, and additional DFT calculations (see the Supporting Information), we propose a possible reaction pathway (Figure 6C). Oxidative addition of 1 to Ni(0) I generates Ni(II) complex II, which undergoes decarbonylation to III.…”

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confidence: 74%

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Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

et al. 2023

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Amines and carboxylic acids are abundant synthetic building blocks that are classically united to form an amide bond. To access new pockets of chemical space, we are interested in the development of amine–acid coupling reactions that complement the amide coupling. In particular, the formation of carbon–carbon bonds by formal deamination and decarboxylation would be an impactful addition to the synthesis toolbox. Here, we report a formal cross-coupling of alkyl amines and aryl carboxylic acids to form C(sp3)–C(sp2) bonds following preactivation of the amine–acid building blocks as a pyridinium salt and N-acyl-glutarimide, respectively. Under nickel-catalyzed reductive cross-coupling conditions, a diversity of simple and complex substrates are united in good to excellent yield, and numerous pharmaceuticals are successfully diversified. High-throughput experimentation was leveraged in the development of the reaction and the discovery of performance-enhancing additives such as phthalimide, RuCl3, and GaCl3. Mechanistic investigations suggest phthalimide may play a role in stabilizing productive Ni complexes rather than being involved in oxidative addition of the N-acyl-imide and that RuCl3 supports the decarbonylation event, thereby improving reaction selectivity.

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confidence: 74%

“…The possibility of 4 facilitating decarbonylation was evaluated, but DFT simulations showed comparable decarbonylation rates for Ni-glutarimide and Ni-phthalimide complexes (Figures S47 and S48). Instead, 4 may play a role in the prevention of unproductive Ni oligomerization ,,, or the formation of off-cycle N -acyl-imide Ni complexes. , …”

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confidence: 99%

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

et al. 2023

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“…However, the key intermediate, bipyridine‐Ni(II)‐amido, was not isolated and studied in these reports. Fortunately, we were able to synthesize a bipyridine‐ligated aryl‐Ni(II)‐amido complex [20] . As shown in Scheme 2, the reductive elimination chemistry of the amidate complex 66 was explored.…”

Section: Resultsmentioning

confidence: 99%

Ni‐Catalyzed Photochemical C−N Coupling of Amides with (Hetero)aryl Chlorides

Song

Nong

et al. 2023

Chemistry A European J

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This paper reports a photochemical CÀ N coupling of abundant, but less reactive aryl chlorides, with structurally diverse primary and secondary amides by Ni-mediated without an external photocatalyst. Under the irradiation of light (390-395 nm) with a soluble organic amine as the base, the reaction allows for the successful transformation of (hetero)aryl chlorides to a wide range of N-aryl amides. More than 60 examples are shown, demonstrating the feasibility and applicability of this protocol in organic synthesis. Mechanic studies indicate that this amidation proceeds via a Ni(I)-Ni(III) catalytic cycle.

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“…This can lead to novel reactivities, such as the formation of C sp2 À C sp3 bonds via cross-electrophile couplings, which is incompatible with noble metal-based catalysts. [51][52][53][54] These metal centers are especially useful for upgrading oxygen-containing molecules, which represent a large number of biomass-derived substrates. For instance, Ni-based catalysts enable CÀ O and CÀ N bond cleavages.…”

Section: Aim and Scope Of The Reviewmentioning

confidence: 99%

Silica‐Supported 1^st Row Transition Metal (Nano)Catalysts: Synthetic and Catalytic Insight

Guerrero‐Ríos¹,

Reina²,

Carmona-Chávez³

et al. 2023

ChemCatChem

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The combination of first‐row transition compounds or nanoparticles with silica‐based supports offers a great possibility for catalyst design. In particular, iron, cobalt and nickel‐based materials rise in attention due to their availability, low cost and interesting reactivity, enabling transformations that are not possible with noble metals. Different support strategies exist where mesoporous silica‐based supports are of particular interest due to their morphology and stability. Their high surface area, tunable pore size and volume and both, thermal and chemical stability, are of great interest in terms of catalyst adsorption and reactants diffusion. The state of the art on the catalyzed transformations to attain fine chemicals is nowadays explored from a sustainable point of view. However, up to now, it is difficult to predict or understand the key features in silica supported first‐row transition metals‐based catalyst, despite the fact that there are widely applied. The rational tailoring of nanosized materials immobilized on silica‐based supports and their application in catalysis requires to be reviewed.

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C(sp3)–H Bond Acylation with N-Acyl Imides under Photoredox/ Nickel Dual Catalysis

Cited by 11 publications

References 10 publications

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Ni‐Catalyzed Photochemical C−N Coupling of Amides with (Hetero)aryl Chlorides

Silica‐Supported 1^st Row Transition Metal (Nano)Catalysts: Synthetic and Catalytic Insight

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C(sp3)–H Bond Acylation with N-Acyl Imides under Photoredox/ Nickel Dual Catalysis

Cited by 11 publications

References 10 publications

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp3–sp2 Carbon–Carbon Bonds

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp3–sp2 Carbon–Carbon Bonds

Ni‐Catalyzed Photochemical C−N Coupling of Amides with (Hetero)aryl Chlorides

Silica‐Supported 1st Row Transition Metal (Nano)Catalysts: Synthetic and Catalytic Insight

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Product

Resources

About

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Silica‐Supported 1^st Row Transition Metal (Nano)Catalysts: Synthetic and Catalytic Insight