Direct Carboxylation of Aryl Tosylates by CO<sub>2</sub> Catalyzed by In situ‐Generated Ni<sup>0</sup>

Rebih, Fatima; Andreini, Manuel; Moncomble, Aurélien; Harrison‐Marchand, Anne; Maddaluno, Jacques; Durandetti, Muriel

doi:10.1002/chem.201503926

Cited by 64 publications

(22 citation statements)

References 101 publications

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“…16 Recently, Durandetti extended the scope of these reactions by using NiBr 2 (bpy) as precatalyst in the absence of halogenated additives (Scheme 12). 39 Although moderate yields were obtained under these reaction conditions, a wide variety of electron-rich or electron-poor aryl tosylates could be employed, including ortho- substituted precursors.…”

Section: Direct Catalytic Carboxylation Of C–heteroatom Bonds With Co2mentioning

confidence: 99%

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

et al. 2016

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The recent years have witnessed the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with CO2 as C1 source, representing potential powerful alternatives to existing methodologies for preparing carboxylic acids, privileged motifs in a myriad of pharmaceuticals and molecules displaying significant biological properties. While originally visualized as exotic cross-coupling reactions, a close look into the literature data indicates that these processes have become a fertile ground, allowing for the utilization of a variety of coupling partners, even with particularly challenging substrate combinations. As for other related cross-electrophile scenarios, the vast majority of reductive carboxylation of organic (pseudo)halides are characterized by their simplicity, mild conditions, and a broad functional group compatibility, suggesting that these processes could be implemented in late-stage diversification. This perspective describes the evolution of metal-catalyzed reductive carboxylation of organic (pseudo)halides from its inception in the pioneering stoichiometric work of Osakada to the present. Specific emphasis is devoted to the reactivity of these coupling processes, with substrates ranging from aryl-, vinyl-, benzyl- to unactivated alkyl (pseudo)halides. Despite the impressive advances realized, a comprehensive study detailing the mechanistic intricacies of these processes is still lacking. Some recent empirical evidence reveal an intriguing dichotomy exerted by the substitution pattern on the ligands utilized; still, however, some elementary steps within the catalytic cycle of these reactions remain speculative, in many instances invoking a canonical cross-coupling process. Although tentative, we anticipate that these processes might fall into more than one distinct mechanistic category depending on the substrate utilized, suggesting that investigations aimed at unraveling the mechanistic underpinnings of these processes will likely bring new and innovative research grounds in this vibrant area of expertise.

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Section: Direct Catalytic Carboxylation Of C–heteroatom Bonds With Co2mentioning

confidence: 99%

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

et al. 2016

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“…[4] Tsuji and co-workers applied [NiCl 2 (PPh 3 ) 2 ]f or the carboxylation of more inert aryl and vinyl chlorides under aC O 2 pressure of 1atm at room temperature. [5] Later,avariety of surrogates,i ncluding sulfonates, [6] ester derivatives, [7] allylic alcohols, [8] and ammonium salts [9] were devised to complement the reaction scope. Notably,a ll of these systems require stoichiometric metal reagents based on Et 2 Zn, Mn, or Zn powder as reducing agents (Scheme 1a).…”

mentioning

confidence: 99%

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO₂ by Dual Visible‐Light–Nickel Catalysis

2017

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We report the efficient carboxylation of bromides and triflates with K 2 CO 3 as the source of CO 2 in the presence of an organic photocatalyst in combination with anickel complex under visible light irradiation at room temperature.T he reaction is compatible with av ariety of functional groups and has been successfully applied to the synthesis and derivatization of biologically active molecules.I np articular, the carboxylation of unactivated cyclic alkyl bromides proceeded well with our protocol, thus extending the scope of this transformation. Spectroscopic and spectroelectrochemical investigations indicated the generation of aN i 0 species as ac atalytic reactive intermediate. Scheme 1. Carboxylation of bromides.

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“…Based on the experimental observations in hand and with reference to previous work on catalytic zincations or Ni–bipy catalyzed reductive carboxylation, we propose a catalytic cycle for the nickel‐catalyzed reaction, as shown in Scheme .…”

Section: Methodsmentioning

confidence: 99%

Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates

Klein

Lechner

Schimmel

et al. 2019

Chemistry A European J

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The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C−X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C−O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C−X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2–1,4‐diazadiene catalyst system, in which 1,4‐diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross‐coupling or electrophilic substitution reactions.

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Direct Carboxylation of Aryl Tosylates by CO₂ Catalyzed by In situ‐Generated Ni⁰

Cited by 64 publications

References 101 publications

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO₂ by Dual Visible‐Light–Nickel Catalysis

Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates

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Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by In situ‐Generated Ni0

Cited by 64 publications

References 101 publications

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO2

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO2

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO2 by Dual Visible‐Light–Nickel Catalysis

Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates

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Product

Resources

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Direct Carboxylation of Aryl Tosylates by CO₂ Catalyzed by In situ‐Generated Ni⁰

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO₂ by Dual Visible‐Light–Nickel Catalysis