Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

Daşkapan, Tahir

doi:10.3998/ark.5550190.0012.520

Cited by 24 publications

(6 citation statements)

References 78 publications

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“…Such a method obviates the need for ligand screening and thus it would operationally simplify the reaction. A promising approach is electrophilic amination in which an aryl nucleophile is directly reacted with an electrophilic nitrogen source to generate the desired aniline . The greatest advantage of this approach is its simplicity, both mechanistically and operationally as it significantly reduces the burden of reaction optimization.…”

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confidence: 99%

Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals

Zhou

Behnke

et al. 2016

J. Am. Chem. Soc.

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Herein we disclose a novel method for the facile transfer of primary (–NH2) and secondary amino groups (–NHR) to heteroaryl- as well as arylcuprates at low temperature without the need for precious metal catalysts, ligands, excess reagents, protecting and/or directing groups. This one-pot transformation allows unprecedented functional group tolerance and it is well-suited for the amination of electron-rich, electron-deficient as well as structurally complex (hetero)arylmetals. In some of the cases, only catalytic amounts of a copper(I) salt is required.

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confidence: 99%

Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals

Zhou

Behnke

et al. 2016

J. Am. Chem. Soc.

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“…Among them, the Buchwald–Hartwig palladium-catalyzed cross-coupling of aryl halides with amines, the Ullmann-type copper-catalyzed cross-coupling of aryl halides with amines, and the Chan–Lam copper-mediated oxidative coupling of aryl metals with amines have proven to be powerful methods for C–N bond formation . An umpolung tactic, involving transition-metal-catalyzed amination of organometallic reagents with electrophilic aminating reagents (e.g., chloroamines and hydroxylamines), provides a valuable complementary approach . Indeed, various organometallic reagents are known to undergo electrophilic amination, including organomagnesiums, -zincs, -tins, -borons, , -silicons, and -titaniums .…”

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confidence: 99%

Copper-Catalyzed Electrophilic Amination of Organolithiums Mediated by Recoverable Siloxane Transfer Agents

Nguyen

Smith

2013

Org. Lett.

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The development and validation of copper-catalyzed, electrophilic amination of aryl and heteroaryl organolithiums with N,N-dialkyl -O-benzoylhydroxylamineshavebeenachievedexploitingrecoverablesiloxanetransferagents. Given the readily availability of organolithium compounds, the mild reaction conditions, the ease of product purification and the ready recovery of the siloxane transfer agents, this transformation comprises a useful tactic to access diverse aryl and heteroaryl amines.

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“…The electrophilic amination reaction was achieved effectively in the presence of Cul as catalyst (10 mol%) and dpca as an additive (10 mol%). To date, various organometallic reagents are identified to implement electrophilic amination, including organomagnesiums, -zincs, -lithiums, and -coppers (Daskapan, 2011). Among of them, the Daskapan group designed several electrophilic amination procedures for organozinc (Daskapan, 2006;Daşkapan and Koca, 2010), organomagnesium (Erdik and Daşkapan 2002;Daşkapan and Cengiz, 2009), and organocopper (Daşkapan and Çiçek, 2017), reagents.…”

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confidence: 99%

Copper-Catalyzed Electrophilic Amination of Diarylcadmium Reagents Utilizing Acetone O-(4- chlorophenylsulphonyl)oxime and Acetone O-(2-naphthylsulphonyl)oxime as Amination Agent

Korkmaz¹

2021

Iğdır Üniversitesi Fen Bilimleri Enstitüsü Dergisi

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In this study, a CuCN catalyzed process of the diarylcadmium compounds by electrophilic amination method was developed using novel acetone O-(4-chlorophenylsulfonyl)oxime and acetone O-(2-naphthylsulfonyl)oxime. Herein, it has been demonstrated that primary arylamines can easily be obtained with good yields at room temperature by CuCN catalyzed amination of diarylcadmium reagents. It was settled down that the yield of primary arylamines depended strongly on the steric and electronic effects of organocadmium reagent and amination agent. In both amination reagents, meta-substituted arylamines were obtained in higher yields than para-substituted aryl amines. All reactions involving organocadmiums were carried out under an argon atmosphere by standard syringe/cannula methods. Amines as reaction products were separated from the reaction mixture as benzamide derivatives and purified and melting points, 1 H NMR analysis determined their accuracy.

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Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

Cited by 24 publications

References 78 publications

Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals

Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals

Copper-Catalyzed Electrophilic Amination of Organolithiums Mediated by Recoverable Siloxane Transfer Agents

Copper-Catalyzed Electrophilic Amination of Diarylcadmium Reagents Utilizing Acetone O-(4- chlorophenylsulphonyl)oxime and Acetone O-(2-naphthylsulphonyl)oxime as Amination Agent

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