Copper-Catalyzed Amination Research Articles

Efficient copper-catalyzed amination of aryl halides with amines and N [sbnd]H heterocycles using rac-BINOL as ligand

A highly efficient copper-catalyzed system using commercially available racemic 1,1′-binaphthyl-2,2′-diol ( rac-BINOL) as the ligand was developed for amination of aryl halides and heteroaryl halides with alkyl amines and N H heterocycles. Good to high yields were obtained for aryl bromides and heteroaryl chlorides. The commercially available rac-BINOL ligand with excellent stability and high efficiency for aryl bromides and heteroaryl chlorides ultimately make this protocol of potentially practical utility.

Regioselective copper-catalyzed amination of bromobenzoic acids using aliphatic and aromatic amines.

A chemo- and regioselective copper-catalyzed cross-coupling procedure for amination of 2-bromobenzoic acids is described. The method eliminates the need for acid protection and produces N-aryl and N-alkyl anthranilic acid derivatives in up to 99% yield. N-(1-Pyrene)anthranilic acid has been employed in metal ion-selective fluorosensing. Titration experiments showed that this pyrene-derived amino acid forms an equimolar complex with Hg(II) in water resulting in selective fluorescence quenching even in the presence of other metal ions such as Zn(II) and Cd(II).

Asymmetric Copper-Catalyzed Allylic Amination and Oxidation Reactions

Asymmetric Copper-Catalyzed Allylic Amination and Oxidation Reactions

Regioselective copper-catalyzed amination of chlorobenzoic acids: synthesis and solid-state structures of N-aryl anthranilic acid derivatives.

[reaction, structure: see text] A chemo- and regioselective copper-catalyzed cross-coupling reaction for effective amination of 2-chlorobenzoic acids with aniline derivatives has been developed. The method eliminates the need for acid protection and produces a wide range of N-aryl anthranilic acid derivatives in up to 99% yield. The amination was found to proceed with both electron-rich and electron-deficient aryl chlorides and anilines and also utilizes sterically hindered anilines such as 2,6-dimethylaniline and 2-tert-butylaniline. The conformational isomerism of appropriately substituted N-aryl anthranilic acids has been investigated in the solid state. Crystallographic analysis of seven anthranilic acid derivatives showed formation of two distinct supramolecular architectures exhibiting trans-anti and unprecedented trans-syn dimeric structures.

Copper‐Catalyzed Aryl Amination in Aqueous Media with 2‐Dimethylaminoethanol Ligand.

AbstractFor Abstract see ChemInform Abstract in Full Text.

General and Efficient Indole Syntheses Based on Catalytic Amination Reactions.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A Mild and Practical Copper‐Catalyzed Amination of Halothiophenes.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Copper-catalyzed aryl amination in aqueous media with 2-dimethylaminoethanol ligand

Copper-catalyzed amination of aryl bromides and iodides under mild conditions has been developed with 2-dimethylaminoethanol as ligand and water as solvent. A variety of hydrophilic and hydrophobic aryl halide substrates have been aminated in good yield with a variety of amino acids, amino alcohols and peptides. This method has successfully N-arylated some hydrophilic amino compounds not available by other methods.

General and Efficient Indole Syntheses Based on Catalytic Amination Reactions

[reaction: see text] Highly flexible and efficient syntheses of the indole backbone are presented starting from o-alkynylhaloarenes. These transformations proceed via a palladium- or a copper-catalyzed amination reaction and a subsequent cyclization reaction in good to excellent yields. Furthermore, a multicatalytic one-pot indole synthesis starting from o-chloroiodobenzene is viable using a single catalyst consisting of an N-heterocyclic carbene palladium complex and CuI.

Synthesis of triarylamines by copper-catalyzed amination of aryl halides

A simple and efficient methodology for the synthesis of triphenylamine (TPA) in a single step has been demonstrated using copper catalyst with a ligand. The effect of parameters such as catalyst precursors, ligands, bases and solvents on activity and selectivity to triphenylamine were studied at 115 °C. Best results were obtained using 2,6-diphenylpyridine as a ligand (94% yield of TPA).

Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides.

1,2-Diphenyl-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene was used as an additive ligand in copper-catalysed amination reactions of halobenzenes with amines in the presence of base to afford the corresponding secondary or tertiary amines in good to excellent yields.

Copper‐Catalyzed Amination of Aromatic Halides with 2‐N,N‐Dimethylaminoethanol as Solvent.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Mild and Efficient Copper‐Catalyzed Amination of Aryl Bromides with Primary Alkylamines.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Copper-catalyzed amination of aromatic halides with 2- N, N-dimethylaminoethanol as solvent

A copper-catalyzed amination of aromatic halides under mild conditions using N, N-dimethylaminoethanol as solvent is described. We have studied this reaction in some detail varying the copper source, base, water content and other parameters including the scope of useful amine and aromatic halide structures. A variety of 4-halo- N, N-cycloalkylanilines and 2- N, N-cycloalkylaminothiophenes were synthesized for further elaboration into chromophores for optoelectronic applications.

Mild and efficient copper-catalyzed amination of aryl bromides with primary alkylamines.

[reaction: see text] An efficient copper-catalyzed amination of aryl bromides with primary alkylamines was developed that uses commercially available diethylsalicylamide as the ligand. This amination reaction can be performed at 90 degrees C in good yield. A variety of functional groups are compatible with these reaction conditions. Preliminary results show that this reaction can be carried out under solvent-free conditions with comparable yields.

Copper-catalyzed amination of aryl halides: single-step synthesis of triarylamines

A simple and efficient methodology for the synthesis of triarylamines in a single step has been demonstrated using a ligand-free CuI catalyst and potassium tertiary butoxide as the base. Use of chelating ligands leads to the formation of triarylamine derivatives selectively (95% yield) with high catalytic activity.

Copper-Catalyzed Coupling of Alkylamines and Aryl Iodides: An Efficient System Even in an Air Atmosphere

[reaction: see text] A mild method for the copper-catalyzed amination of aryl iodides is reported. This operationally simple C-N bond-forming protocol uses CuI as the catalyst and ethylene glycol as ligand in 2-propanol. A variety of functionalized aryl iodides as well as several amines were efficiently coupled using this method. This catalytic amination procedure is relatively insensitive to moisture and can be performed under an air atmosphere with comparable yield. Preliminary results on the amination of aryl bromides are also described.

Copper-catalyzed amination of alkenes and ketones by phenylhydroxylamine

The catalytic activity of a number of copper complexes and salts toward allylic amination of alkenes using phenylhydroxylamine as the nitrogen fragment donor has been investigated. The best catalyst is CuCl2·2H2O, which produces moderate yields of allylamines with high regioselectivity resulting from double bond transposition. A mechanism similar to that for the molybdenum and the FePc systems is proposed. The first step in the catalytic cycle is the formation of nitrosobenzene from the oxidation of phenylhydroxylamine by Cu(II). The next step is an ene reaction of the alkene with PhNO to produce an allylhydroxylamine, which is then reduced to the allylamine product by Cu(I), thus regenerating Cu(II). The same system can also transfer the nitrogen fragment to the α-carbon of cyclic ketones; this is accompanied by dehydrogenation in some cases to produce α-aminated, α,β-unsaturated ketones.

ChemInform Abstract: Copper‐Catalyzed Amination of 1,6‐Hexanediol.

ChemInformVolume 18, Issue 35 Preparative Organic Chemistry ChemInform Abstract: Copper-Catalyzed Amination of 1,6-Hexanediol. R. VULTIER, R. VULTIER Dep. Ind. Eng. Chem., Swiss Fed. Inst. Technol., ETH-Zentrum, 8092 Zuerich, SwitzerlandSearch for more papers by this authorA. BAIKER, A. BAIKER Dep. Ind. Eng. Chem., Swiss Fed. Inst. Technol., ETH-Zentrum, 8092 Zuerich, SwitzerlandSearch for more papers by this authorA. WOKAUN, A. WOKAUN Dep. Ind. Eng. Chem., Swiss Fed. Inst. Technol., ETH-Zentrum, 8092 Zuerich, SwitzerlandSearch for more papers by this author R. VULTIER, R. VULTIER Dep. Ind. Eng. Chem., Swiss Fed. Inst. Technol., ETH-Zentrum, 8092 Zuerich, SwitzerlandSearch for more papers by this authorA. BAIKER, A. BAIKER Dep. Ind. Eng. Chem., Swiss Fed. Inst. Technol., ETH-Zentrum, 8092 Zuerich, SwitzerlandSearch for more papers by this authorA. WOKAUN, A. WOKAUN Dep. Ind. Eng. Chem., Swiss Fed. Inst. Technol., ETH-Zentrum, 8092 Zuerich, SwitzerlandSearch for more papers by this author First published: September 1, 1987 https://doi.org/10.1002/chin.198735130Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume18, Issue35September 1, 1987 RelatedInformation