A new ligand for copper-catalyzed amination of aryl halides to primary(hetero)aryl amines

Jiang, Sheng; Dong, Xinrui; Qiu, Yunli; Chen, Dong; Wu, Xiaoxing

doi:10.1016/j.tetlet.2020.151683

Cited by 15 publications

(7 citation statements)

References 33 publications

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“…Copper-catalyzed C-N coupling reactions have been extensively studied [ 29 ], and Buchwald has reportedly implemented this type of reaction using bromo- or iodobenzenes as substrates progressively, but not with five-membered heterocyclic compounds such as pyrazoles [ 30 , 31 , 32 , 33 , 34 , 35 , 36 ]. As the C-N coupling reaction of 4-halopyrazoles 1 with allyl- or alkylamines bearing β-hydrogen atoms revealed low reactivities in the above investigation ( Table 2 , entries 4–12), the copper-catalyzed reaction of 1 was further studied.…”

Section: Resultsmentioning

confidence: 99%

C4-Alkylamination of C4-Halo-1H-1-tritylpyrazoles Using Pd(dba)2 or CuI

et al. 2020

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Alkylamino coupling reactions at the C4 positions of 4-halo-1H-1-tritylpyrazoles were investigated using palladium or copper catalysts. The Pd(dba)2 catalyzed C-N coupling reaction of aryl- or alkylamines, lacking a β-hydrogen atom, proceeded smoothly using tBuDavePhos as a ligand. As a substrate, 4-Bromo-1-tritylpyrazole was more effective than 4-iodo or chloro-1-tritylpyrazoles. Meanwhile, the CuI mediated C-N coupling reactions of 4-iodo-1H-1-tritylpyrazole were effective for alkylamines possessing a β-hydrogen atom.

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Section: Resultsmentioning

confidence: 99%

C4-Alkylamination of C4-Halo-1H-1-tritylpyrazoles Using Pd(dba)2 or CuI

et al. 2020

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“…■ RECENT REPORTS ON Cu-CATALYZED REACTIONS The development of readily accessible ligands that promote efficient Cu-catalyzed C−N couplings continues with a report from Wu, Jiang, and co-workers. 49 The authors introduced a series of cyclopentane-1,1-dicarboxamide ligands and investigated their utility in the Cu-catalyzed coupling of aqueous ammonia with aryl halides at room temperature (Scheme 16). N,N′-Bis(3,5-dimethoxyphenyl)cyclopentane1,1-dicarboxamide was identified as the optimal ligand, and the coupling was demonstrated for a range of aryl iodides and bromides using CuI (10 mol %), ligand (20 mol %), and Cs 2 CO 3 .…”

Section: ■ Recent Reports On Ni-catalyzed Reactionsmentioning

confidence: 99%

“…The development of readily accessible ligands that promote efficient Cu-catalyzed C–N couplings continues with a report from Wu, Jiang, and co-workers . The authors introduced a series of cyclopentane-1,1-dicarboxamide ligands and investigated their utility in the Cu-catalyzed coupling of aqueous ammonia with aryl halides at room temperature (Scheme ).…”

Section: Recent Reports On Cu-catalyzed Reactionsmentioning

confidence: 99%

Recent Advances in Nonprecious Metal Catalysis

Haibach

Ickes

Wilders

et al. 2020

Org. Process Res. Dev.

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“…Aryl amines can be synthesized by heterogeneous reduction of nitro aryls; − direct amination of halo aryls with ammonia using Cu, − Ni, and Pd , catalytic systems; and selective direct catalyzed amination of CH bonds. , …”

Section: Introductionmentioning

confidence: 99%

Copper(I) Chloride Mediated Amination of Halobenzenes via Azides: Scope, Mechanistic Aspects, and C–C Cleavage Reactions

2023

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Selective azidation−amination of long-chain alkanoyl halobenzenes with sodium azide, promoted by copper(I) chloride, is reported. The protocol is, apart from CuCl and NaN 3 , additive free and allows the isolation of versatile amine−azides. Alkyl cleavage occurs as a side reaction through an unusual Schmidt-type azide insertion adjacent to the carbonyl group, forming alkyl nitriles possibly via radical pathways. Mechanistic studies involving 15 N labeling experiments and test substrates indicate that the reaction occurs via 1-azido-4-alkanoyl benzenes. The amination is applicable for substrates with electron-withdrawing groups and proceeds under mild conditions. The mechanism of the amine formation involves nitrenes. Intermediates were trapped by carrying out the reaction in the presence of the 2,2,6,6-(tetramethylpiperidin-1-yl)oxyl stable radical and characterized by high-resolution mass spectrometry. The intermediates are consistent with earlier mechanistic proposals.

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A new ligand for copper-catalyzed amination of aryl halides to primary(hetero)aryl amines

Cited by 15 publications

References 33 publications

C4-Alkylamination of C4-Halo-1H-1-tritylpyrazoles Using Pd(dba)2 or CuI

C4-Alkylamination of C4-Halo-1H-1-tritylpyrazoles Using Pd(dba)2 or CuI

Recent Advances in Nonprecious Metal Catalysis

Copper(I) Chloride Mediated Amination of Halobenzenes via Azides: Scope, Mechanistic Aspects, and C–C Cleavage Reactions

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