Amination Of Aryl Halides Research Articles

Palladium- and Copper-Catalyzed Aryl Halide Amination, Etherification and Thioetherification Reactions in the Synthesis of Aromatic Heterocycles

This article reviews the use of palladium- and copper-catalyzed aryl halide amination, etherification and thioetherification processes in the synthesis of heteroaromatic molecules. The review is structured by the nature of the key C-X bond being formed, and then by heterocycle type. Where applicable individual heterocycles are further divided into syntheses based on intermolecular, intramolecular and cascade processes. In order to limit the length of the article, processes that do not deliver an aromatic heterocycle from the key C-X bond-forming event are excluded. Processes for the functionalization of intact heteroaromatics are also not included. 1 Introduction 2 Carbon-Nitrogen Bond Formation 2.1 Indoles 2.2 Carbazoles 2.3 Benzimidazoles and Benzimidazolones 2.4 Indazoles and Indazolones 2.5 Pyrroles 2.6 Pyrazoles 2.7 Oxazoles 2.8 Quinolones 2.9 Quinazolines, Quinazolinones and Quinazolinediones 2.10 Phenazines 2.11 Cinnolines 3 Carbon-Oxygen Bond Formation 3.1 Benzofurans 3.2 Benzoxazoles 3.3 Isocoumarins 4 Carbon-Sulfur Bond Formation 4.1 Benzothiophenes 4.2 Benzothiazoles 4.3 Oxathioles 5 Conclusion. © Georg Thieme Verlag Stuttgart · New York.

ChemInform Abstract: Pyrrole‐2‐carbohydrazides as Ligands for Cu‐Catalyzed Amination of Aryl Halides with Amines in Pure Water.

AbstractAryl bromides and iodides are aminated by primary and secondary amines either under microwave irradiation or conventional heating in the same short reaction time.

Carbamic acid 2-trimethylsilylethyl ester as a new ammonia equivalent for palladium-catalyzed amination of aryl halides

Carbamic acid 2-trimethylsilylethyl ester (Teoc-NH 2) serves as an ammonia equivalent in the palladium-catalyzed amination of aryl bromides and aryl chlorides. Anilines with sensitive functional groups can be readily prepared using these amine derivatives.

Heterogeneous Aromatic Amination of Aryl Halides with Arylamines in Water with PS‐PEG Resin‐Supported Palladium Complexes

Catalytic aromatic amination is achieved in water under heterogeneous conditions by the use of immobilized palladium complexes coordinated with the amphiphilic polystyrene-poly(ethylene glycol) resin-supported di(tert-butyl)phosphine ligand. Aromatic amination of aryl halides with diphenylamine and N,N-double arylation of anilines with bromobenzene were found to proceed in water with broad substrate tolerance to give the triarylamines in high yield with high recyclability of the polymeric catalyst beads. Very little palladium leached from the polymeric catalyst under the water-based reaction conditions to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N',N'-tetraaryl-1,1'-biphenyl-4,4'-diamines (TPDs).

Copper‐Mediated Reductive Amination of Aryl Halides with Trimethylsilyl Azide

Copper‐Mediated Reductive Amination of Aryl Halides with Trimethylsilyl Azide

Copper(I) complexes with Schiff base and 1,2-bis(diphenylphosphino)ethane as ligands: Synthesis, structure and catalytic properties for the amination of aryl halide

Some copper(I) complexes of the type [Cu( L)(dppe)]X ( 1– 4) [where L = (3-trifluoromethylphenyl)pyridine-2-ylmethylene-amine; dppe = 1,2-bis(diphenylphosphino)ethane; X = Cl −, CN −, ClO 4 − and BF 4 −] have been synthesized by the condensation of 3-aminobenzotrifluoride with 2-pyridinecarboxaldehyde followed by the reaction with CuCl, CuCN, [Cu(MeCN) 4]ClO 4 and [Cu(MeCN) 4]BF 4 in presence of dppe. The complexes 1– 4 were then characterized on the basis of elemental analysis, IR, UV–Vis and 1H NMR spectral studies. The representative complex of the series 4 has been characterized by single crystal X-ray diffraction which reveal that in complex the central copper(I) ion assumes the irregular pseudo-tetrahedral geometry. The catalytic activity of the complexes was tested and it was found that all the complexes worked as effective catalyst in the amination of aryl halide.

Cover Picture: Heterogeneous Aromatic Amination of Aryl Halides with Arylamines in Water with PS-PEG Resin-Supported Palladium Complexes (Chem. Asian J. 8/2010)

Catalytic aromatic amination …︁ …︁ has been achieved in water under heterogeneous conditions using immobilized palladium complexes of an amphiphilic polystyrene-poly(ethylene glycol) resin-supported di(tert-butyl)phosphine ligand. In their Full Paper on page 1788 ff., Y. Hirai and Y. Uozumi present the aromatic amination of aryl halides with diphenylamine and the N,N-double arylation of anilines with bromobenzene in water with broad substrate tolerance to afford triarylamines, including the optoelectronically active N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′-diamines (TPDs), in high yield with high recyclability of the polymeric catalyst beads.

ChemInform Abstract: β-Hydrogen-Containing Sodium Alkoxides as Suitable Bases in Palladium-Catalyzed Aminations of Aryl Halides.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Examination of the Aromatic Amination Catalyzed by Palladium on Charcoal

AbstractThe Buchwald–Hartwig amination of aryl halides with secondary amines and functionalized aromatic amines catalyzed by solid‐supported palladium is reported. The choices of ligand, base and solvent are crucial for the successful coupling. The amination of aromatic iodides, bromides and chlorides can be easily achieved with palladium on charcoal in the presence of a biphenylphosphane‐type ligand at 80–110 °C. In addition, the palladium on charcoal catalyst is easily separable after the reaction, and reusable several times with only small activity loss.

Pyrrole‐2‐carbohydrazides as Ligands for Cu‐Catalyzed Amination of Aryl Halides with Amines in Pure Water

AbstractPyrrole‐2‐carbohydrazides were synthesized and found to be novel and efficient ligands for the Cu‐catalyzed amination of aryl halides with amines in pure water with high yields. A variety of aryl bromides or iodides could be aminated, promoted by the CuI/N′‐phenyl‐1H‐pyrrole‐2‐carbohydrazide (L13) system, under microwave irradiation or conventional heating without the protection by an inert gas.

Direct amination of aryl halides with ammonia

The traditional homogeneous access to aromatic amine derivatives is a nucleophilic aromatic substitution of the corresponding aryl halides. The halogen atom is usually relatively inert to amination reaction unless it is activated by the presence of electron withdrawing groups. Consequently, there has been particular emphasis over the past decade on the synthesis of metal complexes that are active catalysts for the preparation of aromatic amines. This tutorial review focuses on the use of metal-based complexes for the direct amination of aryl halides with ammonia.

ChemInform Abstract: A Novel Palladium‐Catalyzed Amination of Aryl Halides with Amines Using rac‐P‐Phos as the Ligand.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Heterogenized copper catalysts for the amination of arylhalide: Synthesis, characterization and catalytic applications

This research investigated the synthesis, characterization and catalytic activity of heterogenized copper complexes for the selective amination of aryl halides. Amination reactions using homogeneous copper catalyst systems are not generally selective and it is also difficult to recover the catalyst from the homogeneous system for recycling. To overcome these difficulties, our efforts were directed towards the development of cheaper heterogeneous catalyst systems, which can be easily recovered and recycled. Heterogenized analogs of the homogenous Cu complexes were prepared using two methods: (a) encapsulation of copper complexes in zeolite-Y and (b) tethering of copper complexes on various supports like zeolite-Y, silica, charcoal, or clay. The encapsulated and tethered copper catalysts on zeolite-Y were characterized using EPR, Diffused reflectance UV–vis, XRD, IAS, ICPES, SEM, and TEM. The results confirmed that the copper complexes were truly heterogenized in zeolite-Y support. Encapsulated and tethered copper complexes were tested for amination of aryl iodide. The effects of various reaction parameters were examined using tethered Cu(Phen)(PPh 3)Br-PTA-Y catalyst to determine optimum conditions. A recycle study of encapsulated and tethered Cu catalyst was carried out to test their robustness for possible commercial exploitation.

ChemInform Abstract: A General Palladium‐Catalyzed Amination of Aryl Halides with Ammonia.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

An Efficient Copper‐Catalyzed Amination of Aryl Halides by Aqueous Ammonia

AbstractThe copper(I) bromide/1‐(5,6,7,8‐tetrahydroquinolin‐8‐yl)‐2‐methylpropan‐1‐one (CuBr‐L3) combination catalyzed the cross‐coupling reactions between aryl or heteroaryl halides and aqueous ammonia with high yields to produce primary aromatic or heteroaromatic amines at room temperature or under mild conditions.

ChemInform Abstract: Hemilabile‐Coordinated Copper‐Promoted Amination of Aryl Halides with Ammonia in Aqueous Ethylene Glycol under Atmosphere Pressure.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Copper(I)-Catalyzed Amination of Aryl Halides with Aqueous Ammonia

This new amination method has many advantages: It is operationally simple, utilizes aqueous ammonia which is easy to handle and inexpensive Cu2O as a catalyst. It can be applied to aryl iodides, bromides and chlorides and tolerates a broad range of functionalities. It is highly selective and primary anilines are obtained chemoselectively, thus, without the formation of di- and triarylamines.

A Novel Palladium‐catalyzed Amination of Aryl Halides with Amines Using rac‐P‐Phos as the Ligand

AbstractAn efficient palladium‐catalyzed amination of aryl halides with amines, using rac‐P‐Phos as the ancillary ligand and Pd(OAc)2 as the palladium source is developed. The ligand and all of the synthetic intermediates are stable to air and moisture, allowing the easy handling. The catalyst system performed well for a large number of different substrate combinations in 80–110°C to furnish aromatic amines in high yields.

Palladium-Catalyzed Amination of Aryl Halides with Ammonia

Palladium-Catalyzed Amination of Aryl Halides with Ammonia

CuI-Catalyzed Amination of Arylhalides with Guanidines or Amidines: A Facile Synthesis of 1-H-2-Substituted Benzimidazoles

CuI/L5 (N,N'-dimethylethylenediamine) proves to be an efficient catalyst system for the amination of arylhalides with guanidines. The same catalyst system is then successfully applied to the one-step synthesis of 1-H-2-amino-benzimidazoles through tandem aminations of 1,2-dihaloarenes in modest yields. This methodology is also applicable for the preparation of 1-H or 1-substutituted 2-aryl- or 2-alkyl-benzimidazoles.