4705-13-9

Upstream product

• 108-86-1 bromobenzene 
• 108-91-8 cyclohexylamine 
• 1821-36-9 N-phenyl-2-cyclohexylamine 
• 66003-78-9 triphenylsulfonium trifluoromethanesulfonate 
• 108-94-1 cyclohexanone 
• 122-39-4 diphenylamine 
• 3173-53-3 Cyclohexyl isocyanate 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 108-90-7 chlorobenzene 
• 591-50-4 iodobenzene 

Relevant academic research and scientific papers

Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates

A simple and efficient method for transition-metal-free N-arylation of various amines by triarylsulfonium triflates is described. Both aliphatic and aromatic amines were smoothly converted at 80 °C in the presence of tBuOK or KOH to give the corresponding mono N-arylated products in good to high yields. The molar ratios of the reactants and the choice of bases had a big effect on the reaction. When a large excess of [Ph3S][OTf] and tBuOK were employed for primary amines under the standard conditions, the bis(N-phenyl) products were predominantly formed. This method was also applicable to the synthesis of bioactive N-phenyl amino acid derivatives. The control experiments, the deuterium labelling study, and the presence of regioisomers of N-arylated products when using 4-substituted triarylsulfonium triflates suggested that the reaction might proceed through an aryne intermediate. The present protocol demonstrated that triarylsulfonium salts are versatile arylation reagents in the construction of CAr?N bonds.

Arylation of aniline and amines by Pd-(N-Heterocyclic carbene) complexes

Aminoarenes constitute valuable building blocks in organic synthesis and an essential skeleton ubiquitously found in ligands, agrochemicals, and pharmaceuticals. This synopsis presents recent amination methods using nitrogen-heteroatom bonds as a powerful and versatile platform to rapidly synthesize diverse aminoarenes, with transition-metal catalyzed arene C-H amination. The Buchwald-Hartwig amination has been investigated theoretically and experimentally to examine the scope of possible bases under different reaction conditions. We report examples of the palladium NHC (N-heterocyclic carbene) catalyzed amination of aryl halides with anilines and amines in the presence of dimethoxyethane solvent and potassium tertiary-butoxide as a base.

The synthesis of sterically hindered amines by a direct reductive amination of ketones

An atom-economical methodology for the synthesis of sterically hindered tertiary amines was developed, which is based on complementary Rh- and Ru-catalyzed direct reductive amination of ketones with primary and secondary amines using carbon monoxide as a deoxygenating agent.

Direct reductive amination using triethylsilane and catalytic bismuth(III) chloride

Direct reductive amination (DRA) using triethylsilane (TESH) and catalytic bismuth(III) chloride (BiCl3) is described for the first time. The use of TESH and BiCl3 provides easy handling, low cost, non-toxicity, and a mild Lewis acid activity, thereby meeting the demand for green and sustainable chemistry. The developed DRA is highly chemoselective and applicable to less-basic amines. The experimental results of this study revealed that the developed DRA could be catalyzed by BiCl3, which was gradually reduced to Bi(0) or bismuth with a low valency by TESH, but TESCl, Bi(0), and Bi(0) with TESCl catalyzed the DRA to some extent.

Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride

While pursuing the development of new hydroamination catalysts, a 3-iminophosphine palladium(II) chloride complex [(3IP)PdCl2] was synthesized that has subsequently proven to be an effective precatalyst for the aryl amination of bromoarenes. This (3IP)PdCl2 complex has been utilized in the catalytic aryl amination of both bromobenzene and bromopyridine derivatives, specifically yielding excellent activity in coupling reactions involving bromobenzene, 4-bromotoluene, and 2-bromopyridine. Using a standard set of catalytic conditions, many alkyl and aryl amines have been investigated as coupling partners in the aryl amination of bromoarenes. In general, secondary alkyl amines and ortho-substituted anilines proved to be the best substrates for this reaction, commonly giving quantitative conversion to products, while primary amines and other anilines gave only poor to moderate results. Catalytic screening data, product yields, and full characterization of isolated products are included.

Pyridine-catalyzed double C-N coupling reaction of an isocyanate with two benzynes

A pyridine-catalyzed double C-N bond cross-coupling reaction involving two benzynes with an isocyanate was carried out. The coupling reaction proceeded through a unique pathway involving the formation of an unstable carbamic acid intermediate and facile decarboxylation. Subsequent nucleophilic addition/protonation of in situ prepared amines with benzynes afforded variously substituted diaryl- and triarylamines in moderate to good yields with tolerance of a variety of functional groups. Copyright

Dialkylphosphinoimidazoles as new ligands for palladium-catalyzed coupling reactions of aryl chlorides

N-Aryl-2-(dialkylphosphino)imidazoles and -benzimidazoles are conveniently prepared in one step from the corresponding heterocycles by selective deprotonation and quenching with chlorophosphines. The novel ligands are easily tunable and show good to excellent performance in palladium-catalyzed Suzuki reactions and Buchwald-Hartwig aminations of aryl and heteroaryl chlorides.

Palladium-catalyzed amination of aryl bromides with hindered N-alkyl-substituted anilines using a palladium(I) Tri-tert-butylphosphine bromide dimer

An efficient palladium-catalyzed amination of aromatic bromides with hindered N-alkyl-substituted anilines is described, either using the combination of Pd(OAc)2 and P(t-Bu)3 or a palladium(I) tri-tert-butylphosphine bromide dimer, [Pd(μ-Br)(t-Bu3P)]2, a new, commercially available, and easily handled catalyst.