<i>N</i>-(Hetero)arylations with Metalated (Hetero)aryls: Recent Advances in First-Row Transition-Metal-Mediated Cross-Couplings

Ribaucourt, Aubert; Cossy, Janine

doi:10.1021/acscatal.0c02805

Cited by 18 publications

(7 citation statements)

References 95 publications

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“…Driven by the demand to access low-cost and low-toxicity cross-coupling reactions, transformations meditated by first-row transition metals have acquired significant attention over the years . In particular, the use of first-row transition metals in heterogeneous catalysis would allow an ideal combination of parameters to be reached, such as low cost, reusability, ease of removal, and minimal metal leaching.…”

Section: New Technologies That Could Enable the Application Of Hetero...mentioning

confidence: 99%

Heterogeneous Catalysis for Cross-Coupling Reactions: An Underutilized Powerful and Sustainable Tool in the Fine Chemical Industry?

Vásquez-Céspedes

Betori

Cismesia

et al. 2021

Org. Process Res. Dev.

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Transition-metal-catalyzed cross-coupling reactions are among the most important processes in organic chemistry. For years, the fine chemical industry has looked for a variety of ways to reduce the amounts of transition metals employed in their transformations, particularly in cross-coupling reactions. One interesting alternative to consider is the use of heterogeneous catalysis because of its potential benefits of low metal levels postreaction and reusability. Numerous examples of the use of heterogeneous catalysis will be described in this review that highlight its advantages over more commonly employed homogeneous catalysts. Despite their great potential, the past decade has seen a decrease in the use of heterogeneous catalysts for cross-coupling reactions in the fine chemical industry, fueled by the perception of difficult reaction understanding and reproducibility. With the emergence of a new generation of supported metal catalysts, first-row transition metal catalysis, and continuous flow technology, a variety of tools have been developed to change this reluctance toward heterogeneous catalysis for cross-coupling reactions in the fine chemical industry. We hope that this review captures the attention of the participants in the fine chemical field to consider and implement heterogeneous catalysis for cross-coupling reactions.

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Section: New Technologies That Could Enable the Application Of Hetero...mentioning

confidence: 99%

Heterogeneous Catalysis for Cross-Coupling Reactions: An Underutilized Powerful and Sustainable Tool in the Fine Chemical Industry?

Vásquez-Céspedes

Betori

Cismesia

et al. 2021

Org. Process Res. Dev.

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“…To our delight, similar to the transformation of 3a′ to 2a′, a complete conversion of 4a′ to 2a′ in the presence of Ph 2 CN 2 could be accomplished within 3 h as demonstrated by the 1 H NMR monitoring process (Fig. S66 in ESI †), which was further confirmed by 13 C NMR analysis (Fig. S67 in ESI †).…”

Section: Paper Dalton Transactionsmentioning

confidence: 56%

“…[10][11][12] Afterwards, the first-row transition metals including Fe, Co, and Ni were utilized to build the C aryl -N bonds. 13 The utilization of arenes and (hetero)arenes in the cross-coupling reactions is evidently an atom-and step-economical strategy for the synthesis of amino derivatives. [14][15][16] Brasche and Buchwald 17 discovered intramolecular amination catalyzed by Cu(OAc) 2 using oxygen as the oxidant.…”

Section: Introductionmentioning

confidence: 99%

Aryl C–H bond functionalization with diphenyldiazomethane induced by rare-earth metal alkyl complexes

Guo¹,

Rajeshkumar²,

Zhu³

et al. 2023

Dalton Trans.

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“…Despite the satisfactory performance, the palladium catalyst has its own limitations such as high cost, toxicity, low abundance, etc., resulting in the need for sustainable, cost-effective alternatives, thereby facilitating the development of first-row transition metal (Cu, Fe, Co, Ni, etc. ) based catalysts. Among these, the Cu-based catalyst , has been reported to be versatile and productive toward the C(sp 2 )-heteroatom cross-coupling reaction as copper has accessibility to four stable oxidation states of 0 to +3 .…”

Section: Introductionmentioning

confidence: 99%

Multifunctional Catalysis by a One-Dimensional Copper(II) Metal Organic Framework Containing Pre-existing Coordinatively Unsaturated Sites: Intermolecular C–N, C–O, and C–S Cross-Coupling; Stereoselective Intramolecular C–N Coupling; and Aziridination Reactions

et al. 2022

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The coordinatively unsaturated sites (CUS) are vital in metal-centered catalysis. Metal–organic frameworks (MOFs) provide a unique opportunity to generate and stabilize CUS due to their robust structure. Generally, the generation of CUS in MOFs needs prior activation under heat and high vacuum to remove labile molecules occupying the catalytic sites. Herein, we report a solvothermal synthesis of a ready-to-use copper MOF containing accessible pre-existing CUS that does not need activation. The single crystal X-ray diffraction structure reveals a square planar Cu(II) center with two N-methylimidazoles (Mim) and one benzenedicarboxylic acid (BDC) with the formula unit [CuII(BDC)(Mim)2] n (Cu-1D) forming an infinite one-dimensional (1D) chain along the c axis. The 1D chains are stabilized by noncovalent π–π, CH···π, and H-bonding interaction to give 2D (sheet-like) and 3D networks in the solid state. The quantification of non-covalent interaction is studied by Hirshfeld surface analysis, and the formation of a higher architecture in the solid state is confirmed by SEM analysis. The reported Cu-1D MOF acts as a solid heterogeneous catalyst and exhibits efficient catalytic activity in intermolecular and intramolecular cross-coupling reactions. Intermolecular C-heteroatom cross-coupling of a variety of N-heterocycles, aliphatic, aromatic, alicyclic amines and amides (C–N), phenols (C–O), and thiols (C–S) with aryl halides (halide = I, Br) was achieved with 70 to 95% yield, better than the state-of-the-art Cu-based homogenous system. The C–N coupling catalytic cycle is initiated by the in situ reduction of Cu(II) by KOH/DMSO to Cu(I) species. Subsequently, Cu(I) undergoes oxidative addition followed by reductive elimination to form a cross-coupled product. High stereoselectivity was found for the intramolecular C–N coupling reaction to give tetrahydroquinoxalines with an enantiomeric excess (ee) of more than 99%. For a broader application, Cu-1D was applied as the catalyst for the synthesis of a library of aziridines that gives yields of up to 99% with more than 93% recyclability for each cycle.

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N-(Hetero)arylations with Metalated (Hetero)aryls: Recent Advances in First-Row Transition-Metal-Mediated Cross-Couplings

Cited by 18 publications

References 95 publications

Heterogeneous Catalysis for Cross-Coupling Reactions: An Underutilized Powerful and Sustainable Tool in the Fine Chemical Industry?

Heterogeneous Catalysis for Cross-Coupling Reactions: An Underutilized Powerful and Sustainable Tool in the Fine Chemical Industry?

Aryl C–H bond functionalization with diphenyldiazomethane induced by rare-earth metal alkyl complexes

Multifunctional Catalysis by a One-Dimensional Copper(II) Metal Organic Framework Containing Pre-existing Coordinatively Unsaturated Sites: Intermolecular C–N, C–O, and C–S Cross-Coupling; Stereoselective Intramolecular C–N Coupling; and Aziridination Reactions

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