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• 553-94-6 4-bromo-m-xylene 
• 100-46-9 benzylamine 
• 95-72-7 2-chloro-1,4-dimethyl-benzene 
• 1122-42-5 2-iodo-p-xylene 
• 95-78-3 2,5-Dimethylaniline 
• 100-52-7 benzaldehyde 
• 108837-62-3 N-(2,5-dimethylphenyl)benzimidamide 
• 100-51-6 benzyl alcohol 
• 46727-16-6 N-benzylidene-2,5-dimethylaniline 

Relevant academic research and scientific papers

Selective C-C bonds formation, N-alkylation and benzo[d]imidazoles synthesis by a recyclable zinc composite

Earth abundant metals are much less expensive, promising, valuable metals and could be served as catalysts for the borrowing hydrogen reaction, dehydrogenation and heterocycles synthesis, instead of noble metals. The uniformly dispersed zinc composites were designed, synthesized and carefully characterized by means of XPS, EDS, TEM and XRD. The resulting zinc composite showed good catalytic activity for the N-alkylation of amines with amines, ketones with alcohols in water under base-free conditions, while unsaturated carbonyl compounds could also be synthesized by tuning the reaction conditions. Importantly, it was the first time to realize the synthesis of 2-aryl-1H-benzo[d]imidazole derivatives by using this zinc composite under green conditions. Meanwhile, this zinc catalyst could be easily recovered and reused for at least five times.

Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation

A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]

Base-Mediated Amination of Alcohols Using Amidines

Novel and efficient base-mediated N-alkylation and amidation of amidines with alcohols have been developed, which can be carried out in one-pot reaction conditions, which allows for the synthesis of a wide range of N-alkyl amines and free amides in good to excellent yields with high atom economy. In contrast to borrowing hydrogen/hydrogen autotransfer or oxidative-type N-alkylation reactions, in which alcohols are activated by transition-metal-catalyzed or oxidative aerobic dehydrogenation, the use of amidines provides an effective surrogate of amines. This circumvents the inherent necessity in N-alkylation of an oxidant or a catalyst to be stabilized by ligands.

Base-mediated cascade amidination/: N -alkylation of amines by alcohols

A base-mediated cascade amidination/N-alkylation reaction of amines by alcohols has been developed. For the first time, nitriles have been identified as an efficient and benign water acceptor reagent in N-alkylation. Notably, the procedure tolerates a series of functional groups, such as methoxyl, halo, vinyl and hetero groups, providing a convenient method to construct different substituted diamino compounds, 15N labeled amine and could be scaled up to 1 mol scale offering 138.7 g of the desired product in good yield in one-pot. Mechanistic studies provided strong evidence for the amidination of amines with nitriles facilitated by t-BuOK.

Alcohol Amination Catalyzed by Copper Powder as a Self-Supported Catalyst

Catalytic alcohol amination is a sustainable reaction for N-alkyl amine synthesis. Homogeneous and supported copper catalysts have long been studied for this reaction and have given some impressive results. In this study, copper powder is found to behave as an active catalyst for alcohol amination, giving better catalytic performance than metal-oxide-supported nanocopper catalysts. Catalyst characterization suggests that the copper powder can be considered as a self-supported nanocopper catalyst (i.e., nanocopper supported on copper particles). These results might promote the study of unsupported transition metal powders in sustainable catalytic reactions.

BINAP-copper supported by hydrotalcite as an efficient catalyst for the borrowing hydrogen reaction and dehydrogenation cyclization under water or solvent-free conditions

A BINAP-Cu system supported by hydrotalcite has been developed and proved to be a highly efficient catalyst for the atom-efficient and green borrowing hydrogen reaction and dehydrogenative cyclization. This BINAP-Cu complex supported by hydrotalcite is highly air-stable and can be recycled at least five times under solvent-free conditions. Notably, 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives could be synthesized from alcohols in only one step with water as the solvent for the first time. This provided a much greener and efficient catalytic method towards the synthesis of functionalized amines, ketones and 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives with high yields under water or solvent-free conditions.

Direct access to: N -alkylated amines and imines via acceptorless dehydrogenative coupling catalyzed by a cobalt(ii)-NNN pincer complex

A simple, phosphine-free Co(ii)-NNN pincer complex catalyzed direct N-alkylation of anilines with alcohols via hydrogen auto-transfer (HA) and selective acceptorless dehydrogenative coupling (ADC) of benzylamines with alcohols affording imines with the liberation of molecular hydrogen and water is reported.

Synthesis of 3-Arylbenzofuran-2-ylphosphines via Rhodium-Catalyzed Redox-Neutral C-H Activation and Their Applications in Palladium-Catalyzed Cross-Coupling of Aryl Chlorides

A new class of aryl-heteroarylphosphines, 3-arylbenzofuran-2-ylphosphines, was synthesized by [Cp?Rh(III)]-catalyzed redox-neutral cyclization of N-phenoxyacetamides with 1-alkynylphosphine sulfides and oxides followed by reduction. This step-economic reaction proceeds in excellent regioselectivity with a broad substrate scope. The application of the resulting air-stable trivalent-phosphine containing dicyclohexylphosphino moiety in palladium-catalyzed Suzuki-Miyaura coupling and Buchwald-Hartwig amination of aryl chlorides is also described.

Tunable Triazole-Phosphine-Copper Catalysts for the Synthesis of 2-Aryl-1H-benzo[d]imidazoles from Benzyl Alcohols and Diamines by Acceptorless Dehydrogenation and Borrowing Hydrogen Reactions

Triazole-phosphine-copper complexes (TAP?Cu) have been synthesized and applied as tunable and efficient catalysts for the selective synthesis of fluoro-substituted 2-aryl-1H-benzo[d]imidazole and 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives from simple alcohols in only one step. TAP?Cu exhibited excellent and tunable catalytic activity for both dehydrogenation and borrowing hydrogen reactions with more than 80 examples being demonstrated for the first time. It was observed that the ligand played a critical role in catalyst activity. Mechanistic studies and deuterium labeling experiments indicated that the reactions proceeded by an initial and reversible alcohol dehydrogenation resulting in a copper hydride intermediate. This was also supported by the direct observation of a diagnostic copper hydride signal by solid-state infrared spectroscopy. The TAP?Cu-H complex showed absorptions at 912 cm?1 that could be assigned to copper?hydride stretches. Furthermore, the direct trapping of an intermediate bisimine was also successfully performed. (Figure presented.).

Tert-Butyl Hydroperoxide and Tetrabutylammonium Iodide-Promoted Free Radical Cyclization of α-Imino-N-arylamides and α-Azido-N-arylamides

The oxidizing system of tert-butyl hydroperoxide (TBHP) and tetrabutylammonium iodide (TBAI) is capable of generating α-(arylaminocarbonyl)iminyl radicals from ethyl 2-(N-arylcarbamoyl)-2-iminoacetates. These iminyl radicals preferably undergo intramolecular ipso attack on the benzene ring to give azaspirocyclohexadienyl radicals, which are readily captured by molecular oxygen under an oxygen atmosphere to yield azaspirocyclohexadienones. In the absence of oxygen, the reaction affords quinoxalin-2-one products. This oxidizing system is also effective to convert α-aryl-α-azido-N-arylamides to the corresponding iminyl radicals under basic conditions (sodium tert-butoxide, t-BuONa), and the subsequent cyclization of these iminyl radicals results in the formation of azaspirocyclohexadienone products in high yields under an oxygen atmosphere. Plausible mechanisms are proposed to rationalize the experimental results, and factors influencing the reactions are discussed.