CuI/2-Aminopyridine 1-Oxide Catalyzed Amination of Aryl Chlorides with Aliphatic Amines

Liu, Wenjie; Xu, Jiamin; Chen, Xiahong; Zhang, Fuxing; Xu, Zhifeng; Wang, Deping; He, Yueping; Xia, Xiaohong; Zhang, Xin; Liang, Yun

doi:10.1021/acs.orglett.0c02672

Cited by 22 publications

(18 citation statements)

References 120 publications

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“…A limitation of Cu-catalyzed C–N cross-coupling reactions is their lower efficiency toward less reactive aryl chloride substrates. This limitation was addressed with the introduction of an oxalic diamide ligand scaffold by Ma et al Recently, a new class of 2-aminopyridine-1-oxide ligands was disclosed by Liu and co-workers as effective ligands for the Ullman coupling of aryl chlorides . A variety of aryl and heteroaryl chlorides were coupled with an assortment of primary and cyclic secondary amines in moderate to excellent yields (Scheme ).…”

Section: Recent Reports On Cu-catalyzed Reactionsmentioning

confidence: 99%

“…This limitation was addressed with the introduction of an oxalic diamide ligand scaffold by Ma et al 56 Recently, a new class of 2-aminopyridine-1-oxide ligands was disclosed by Liu and co-workers as effective ligands for the Ullman coupling of aryl chlorides. 57 A variety of aryl and heteroaryl chlorides were coupled with an assortment of primary and cyclic secondary amines in moderate to excellent yields (Scheme 38). However, incomplete conversion of the aryl chloride was observed with more sterically hindered acyclic secondary amines and morpholine.…”

Section: ■ Recent Reports On Ni-catalyzed Reactionsmentioning

confidence: 99%

“…N,N,N′,N′-tetramethylethylenediamine (TMEDA) is commonly used as an effective additive in iron catalysis to promote high conversion and selectivity. Neidig and co-workers used 57 Fe Mossbauer spectroscopy to monitor in situ key reactive iron intermediates involved in the iron-catalyzed hydromagnesiation of styrene derivatives in the presence of TMEDA. 85 Their studies revealed the formation of a TMEDA−Fe(II)−bis(alkyl) complex, a key structure that undergoes selective reduction to form the catalytically active styrene-stabilized Fe(0) complex (Scheme 56).…”

Section: ■ Recent Reports On Ni-catalyzed Reactionsmentioning

confidence: 99%

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Recent Advances in Nonprecious Metal Catalysis

Buono

Nguyen

et al. 2021

Org. Process Res. Dev.

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This review summarizes recent developments and synthetic applications of nonprecious metal catalysis (NPMC) published between July and October 2020. It is the next installment of the review series on this topic briefing recent advancements in the synthetic utility of Ni, Cu, and Fe catalysis. The continued increase in the number of publications in this area attests to the wide interest among academic and industrial research laboratories in advancing the catalytic applications of these earth-abundant metals.

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Section: Recent Reports On Cu-catalyzed Reactionsmentioning

confidence: 99%

Section: ■ Recent Reports On Ni-catalyzed Reactionsmentioning

confidence: 99%

Section: ■ Recent Reports On Ni-catalyzed Reactionsmentioning

confidence: 99%

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Recent Advances in Nonprecious Metal Catalysis

Buono

Nguyen

et al. 2021

Org. Process Res. Dev.

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“…The pioneering work of Ullmann and Goldberg that introduced copper for the arylation of amines/amides using an aryl iodide to form a C(sp 2 )–N bond is captivating. Heteroatom-arylated compounds containing C–heteroatom bonds (C–N, C–S, and C–O) are important for the synthesis of agrochemicals, pharmaceuticals, and biologically active compounds. − However, the conventional methods to form such bonds use pre-functionalized reactants and also produce an significant amount of hazardous waste . Migita et al reported the use of a palladium catalyst for the reaction between an aryl halide and aminostannate to form a C(sp 2 )–N bond.…”

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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“…Copper-catalyzed amination can smoothly occur by using some O, O; N, O; and N, N ancillary ligands. 3 Although these ligands can adequately accelerate the coupling reaction, they are difficult to recycle and reuse, and large-scale production is costly, especially for some expensive ligands and complexes formed by ligand–copper( i ) or ( ii ). 4 Therefore, it is necessary to develop copper-catalyzed Ullmann coupling reaction ligands with recyclability and practical application value, although some recyclable ligands have been reported.…”

mentioning

confidence: 99%