75366-13-1

Upstream product

• 6906-25-8 N-(3-methylbenzylidene)aniline 
• 75366-05-1 3-methylbicyclo<4.1.0>hepta-1,3,5-triene 
• 62-53-3 aniline 
• 75366-04-0 2-methyl-1H-cyclopropabenzene 
• 587-03-1 3-methylbenzyl alcohol 
• 21175-64-4 1,1-dideuteriophenylmethanol 
• 620-23-5 m-tolyl aldehyde 
• 98-95-3 nitrobenzene 
• 620-19-9 1-chloromethyl-3-methyl-benzene 
• 103-70-8 Formanilid 
• 756819-35-9 2-(N-anilino)-2-(3-methylphenyl)acetonitrile 
• 32578-31-7 3-tolyl triflate 
• 103-01-5 N-Phenylglycine 
• 1527-91-9 N-phenylbenzamidine 

Downstream Products

• 913169-23-0 N-allyl-N-(3-methylbenzyl)aniline 
• 913169-27-4 2-allyl-N-(3-methylbenzyl)aniline 
• 18818-40-1 2-(3-methylphenyl)-4(3H)-quinazolinone 

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.

Tungsten-Catalyzed Direct N-Alkylation of Anilines with Alcohols

The implementation of non-noble metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of non-noble metal catalysts. Herein, we report a tungsten-catalyzed N-alkylation reaction of anilines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)4 (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible in-situ catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.

Cooperative catalysis of molybdenum with organocatalysts for distribution of products between amines and imines

Multi-amino groups and nitrogen donors compound was discovered as an organocatalyst for N-alkylation of alcohols with amines in the presence of Mo(CO)6. The Mo(CO)6/organocatalyst binary system has shown to be a highly active catalyst for the N-alkylation reaction between alcohols and amines with excellent tolerance of variable starting materials bearing different functional groups. Of particular note, this method possessing a superiority selectivity in the synthesis of N-alkylated amines or imines, which can be controlled by the reaction temperature. The cooperative catalysis mechanism in combination of Mo(CO)6 with organocatalyst was elucidated by control experiments.

Ruthenium(ii) complexes with N-heterocyclic carbene-phosphine ligands for theN-alkylation of amines with alcohols

Metal hydride complexes are key intermediates forN-alkylation of amines with alcohols by the borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols and the hydrogenation of imines. Herein we report ruthenium(ii) complexes with hetero-bidentate N-heterocyclic carbene (NHC)-phosphine ligands, which realize smart pathway selection in theN-alkylated reactionviareactivity tuning of [Ru-H] species by hetero-bidentate ligands. In particular, complex6cbwith a phenyl wingtip group and BArF?counter anion, is shown to be one of the most efficient pre-catalysts for this transformation (temperature is as low as 70 °C, neat conditions and catalyst loading is as low as 0.25 mol%). A large variety of (hetero)aromatic amines and primary alcohols were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. Notably, aliphatic amines, challenging methanol and diamines could also be transformed into the desired products. Detailed control experiments and density functional theory (DFT) calculations provide insights to understand the mechanism and the smart pathway selectionvia[Ru-H] species in this process.

Effect of the ancillary ligand in N-heterocyclic carbene iridium(III) catalyzed N-alkylation of amines with alcohols

A series of air-stable N-heterocyclic carbene (NHC) Ir(III) complexes (Ir1-6), bearing various combinations of chlorine, pyridine and NHC ligands, were assayed for the N-alkylation of amines with alcohols. It was found that Ir3, with two monodentate 1,3-bis-methyl-imidazolylidene (IMe) ligands, emerged as the most active complex. A large variety of amines and primary alcohols were efficiently converted into mono-N-alkylated amines in 53–96% yields. As a special highlight, for the challenging MeOH, selective N-monomethylation could be achieved using KOH as a base under an air atmosphere. Moreover, this catalytic system was successfully applied to the gram-scale synthesis of some valuable compounds.

Enhanced Hydride Donation Achieved Molybdenum Catalyzed Direct N-Alkylation of Anilines or Nitroarenes with Alcohols: From Computational Design to Experiment

An example of homogeneous Mo-catalyzed direct N-alkylation of anilines or nitroarenes with alcohols is presented. The DFT aimed design suggested the easily accessible bis-NHC-Mo(0) complex features a strong hydride-donating ability, achieving effective N-alkylation of anilines or challenging nitroarenes with alcohols. The enhanced hydride-donating strategy should be useful in designing highly active systems for borrowing hydrogen transformations.

Convenient and Reusable Manganese-Based Nanocatalyst for Amination of Alcohols

The development of new sustainable nanocatalytic systems for green chemical synthesis is a growing area in chemical science. Herein, a reusable heterogeneous N-doped graphene-based manganese nanocatalyst (Mn@NrGO) for selective N-alkylation of amines with alcohols is described. Mechanistic studies illustrate that the catalytic reaction follows a domino dehydrogenation-condensation-hydrogenation sequence of alcohols and amines with the formation of water as the sole by-product. The scope of the reaction is extended to the synthesis of pharmaceutically important N-alkylated amine intermediates. The heterogeneous nature of the catalyst made it easy to separate for long-term performance, and the recycling study revealed that the catalyst was robust and retained its activity after several recycling experiments.

Transfer Hydrogenation of Ketones and Imines with Methanol under Base-Free Conditions Catalyzed by an Anionic Metal-Ligand Bifunctional Iridium Catalyst

An anionic iridium complex [Cp*Ir(2,2′-bpyO)(OH)][Na] was found to be a general and highly efficient catalyst for transfer hydrogenation of ketones and imines with methanol under base-free conditions. Readily reducible or labile substituents, such as nitro, cyano, and ester groups, were tolerated under present reaction conditions. Notably, this study exhibits the unique potential of anionic metal-ligand bifunctional iridium catalysts for transfer hydrogenation with methanol as a hydrogen source.

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.