46425-95-0

Upstream product

• 100-52-7 benzaldehyde 
• 95-55-6 2-amino-phenol 
• 928642-45-9 6-diazo-2-cyclohexen-1-one 
• 100-46-9 benzylamine 
• 88-75-5 2-hydroxynitrobenzene 
• 100-51-6 benzyl alcohol 
• 2876-13-3 N-benzylpyridinium chloride 
• 100-44-7 benzyl chloride 
• 1360999-17-2 (2S,4S)-4-methyl-2,4-diphenyl-1,2,3,4-tetrahydroquinolin-8-ol 
• 1624-53-9 2-(benzylideneamino)phenol 
• 87271-67-8 N-Benzyl-N'-phenoxyurea 
• 33054-04-5 phenylacetyl azide 
• 3230-45-3 (E)-N-benzylidene-2-hydroxyaniline 
• 355401-57-9 (3aR,7aS)-6-iodo-2,2-dimethyl-3a,4,5,7a-tetrahydro-1,3-benzodioxol-5-one 

Downstream Products

• 87707-51-5 3-benzylbenzoxazoline-2-thione 
• 77434-65-2 4-benzyl-3,4-dihydro-2H-1,4-benzoxazine-2-acetonitrile 
• 77434-56-1 methyl 4-benzyl-3,4-dihydro-2H-1,4-benzoxazine-2-acetate 
• 77434-66-3 (4-Benzyl-2-phenyl-3,4-dihydro-2H-benzo[1,4]oxazin-2-yl)-acetic acid methyl ester 
• 106201-19-8 2-{Benzyl-[(E)-3-(4-nitro-phenyl)-allyl]-amino}-phenol 
• 77434-68-5 (4-Benzyl-2-phenyl-3,4-dihydro-2H-benzo[1,4]oxazin-2-yl)-acetonitrile 
• 106201-13-2 (E)-4-[Benzyl-(2-hydroxy-phenyl)-amino]-3-(4-chloro-phenyl)-but-2-enoic acid methyl ester 
• 176164-99-1 4-benzyl-2-vinyl-1,4-benzoxazine 
• 881653-57-2 N-benzyl-2-((tert-butyldimethylsilyl)oxy)aniline 
• 881653-09-4 N-benzyl-2-(triethylsilyloxy)aniline 
• 106201-34-7 2-(2,2-Diphenyl-vinyl)-3,4-dihydro-2H-benzo[1,4]oxazine 
• 77434-71-0 methyl 3,4-dihydro-3-phenyl-2H-1,4-benzoxazine-2-acetate 
• 106201-21-2 2-(4-Phenethyl-3,4-dihydro-2H-benzo[1,4]oxazin-2-yl)-ethanol 
• 106201-35-8 (4-Benzyl-3,4-dihydro-2H-benzo[1,4]oxazin-2-yl)-acetyl chloride 

Relevant academic research and scientific papers

BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant

A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.

Iron(0)-Catalyzed Transfer Hydrogenative Condensation of Nitroarenes with Alcohols: A Straightforward Approach to Benzoxazoles, Benzothiazoles, and Benzimidazoles

The iron-catalyzed hydrogen transfer strategy has been applied to the redox condensation of o-hydroxynitrobenzene with alcohol, leading to the formation of benzoxazole derivatives. A wide range of 2-substituted benzoxazoles were synthesized in good to excellent yields without the addition of an external redox agent. A series of control experiments provided a plausible mechanism. Furthermore, the reaction system was successfully extended to the synthesis of benzothiazoles and benzimidazoles.

One-pot synthesis of secondary amine via photoalkylation of nitroarenes with benzyl alcohol over Pd/monolayer H1.07Ti1.73O4·H2O nanosheets

The photoalkylation of nitroarenes with benzyl alcohols in one pot at room temperature and 1 atm N2 was achieved over the Pd/H1.07Ti1.73O4·H2O nanosheets. The sample shows efficient photocatalytic activity with high conversion of nitrobenzene (99%) and selectivity of secondary amine (85%). This flexible photocatalytic system is also applicable to other nitroarenes with high efficiency. Results of in situ FTIR, DRS, and in situ ESR revealed that the benzyl alcohol and nitrobenzene molecules can bind with the surface Lewis and Br?nsted acid sites in the catalyst via the H–O?Ti and NO2?H–O–Ti species. The formation of surface coordination species results in not only the activation of reactant molecules via surface electron transfer, but also the expanded visible light absorption of the catalyst. Moreover, in situ ESR suggested that the surface coordination can also facilitate the formation of oxygen vacancies in catalysts, which can greatly promote the exposure of Lewis sites and enhance the activation of reactant molecules. Finally, a possible hydrogen transfer strategy over the sample is proposed on a molecular level.

Design, Synthesis, and Biological Activity of New N -(Phenylmethyl)-benzoxazol-2-thiones as Macrophage Migration Inhibitory Factor (MIF) Antagonists: Efficacies in Experimental Pulmonary Hypertension

Macrophage migration inhibitory factor (MIF) is a key pleiotropic mediator and a promising therapeutic target in cancer as well as in several inflammatory and cardiovascular diseases including pulmonary arterial hypertension (PAH). Here, a novel series of N-(phenylmethyl)-benzoxazol-2-thiones 5-32 designed to target the MIF tautomerase active site was synthesized and evaluated for its effects on cell survival. Investigation of structure-activity relationship (SAR) particularly at the 5-position of the benzoxazole core led to the identification of 31 that potently inhibits cell survival in DU-145 prostate cancer cells and pulmonary endothelial cells derived from patients with idiopathic PAH (iPAH-ECs), two cell lines for which survival is MIF-dependent. Molecular docking studies helped to interpret initial SAR related to MIF tautomerase inhibition and propose preferred binding mode for 31 within the MIF tautomerase active site. Interestingly, daily treatment with 31 started 2 weeks after a subcutaneous monocrotaline injection regressed established pulmonary hypertension in rats.

Magnetic nanoparticle-supported phosphine gold(i) complex: A highly efficient and recyclable catalyst for the direct reductive amination of aldehydes and ketones

The direct reductive amination of aldehydes and ketones has been achieved in dichloromethane at room temperature by using a magnetic nanoparticle-supported phosphine gold(i) complex [Fe3O4@SiO2-P-AuCl] as the catalyst and ethyl Hantzsch ester as the hydrogen source, yielding a variety of secondary amines in excellent yields under neutral conditions. The new heterogeneous gold catalyst can be prepared by a simple procedure from commercially readily available reagents and can easily be separated from the reaction mixture by applying an external magnet and recycled at least 10 times without any loss of activity.

S8-Mediated Cyclization of 2-Aminophenols/thiophenols with Arylmethyl Chloride: Approach to Benzoxazoles and Benzothiazoles

A metal-free approach to benzazoles from arylmethyl chlorides and 2-mercaptan/2-hydroxyanilines using elemental sulfur as a traceless oxidizing agent has been developed. The reactions proceeded in good to excellent yields, exhibiting good functional groups tolerance and gram-scale ability. A key mechanistic investigation indicated that the key intermediate trisulfide 6, which was characterized by NMR, HRMS and crystal X-ray crystallography, was separated in the reaction prior to the formation of the product.

Diethylenetriamine-Mediated Direct Cleavage of Unactivated Carbamates and Ureas

Diethylenetriamine is effective for the direct cleavage of unactivated carbamates and ureas without additional reagents and catalysts. Various carbamates and ureas were cleaved to afford products in good yield, and the reactions were not affected by air or moisture. Unique chemoselective cleavage of carbamate and urea in the presence of amides was also achieved.

Metal-free reductive amination of aldehydes for the synthesis of secondary and tertiary amines

Reductive amination of aldehydes to produce secondary amines at room-temperature by in situ generated benzimidazoline is discussed. The bonus of the reaction is the formation of pharmaceutically important benzimidazole as a by-product in good yield, which can be recovered from the reaction mixture by simple filtration. The product, secondary amine, is transformed to tertiary amine in the same pot.

Nano-sized NiLa2O4 spinel-NaBH4-mediated reduction of imines to secondary amines

Nano-sized NiLa2O4 spinel was produced by thermal decomposition of Ni-La compounds via a sol-gel method. The well-crystallized spinel structure was formed after calcination at 750 °C. The physicochemical properties of the spinel were investigated using differential thermal analysis, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and particle size distribution analysis. The results show that the nanoparticles have regular shapes with well-defined crystal faces and consist of uniform quasi-spherical crystallites of average size 40 nm. The refined unit cell parameters are a = 3.861205 ? and c = 12.6793 ?. This new nano-sized NiLa2O4 spinel is an efficient heterogeneous catalyst for the selective conversion of imines to the corresponding secondary amines in the presence of NaBH4 as a reducing agent, in good to excellent yields. All the reactions were completely chemoselective at room temperature and had relatively short reaction times. Secondary amines with different aryl groups, including those bearing electron-withdrawing or electron-donating groups, were obtained under the optimum reaction conditions. The catalyst was readily recovered and was recycled four times with no significant loss of catalytic activity.

A Pd-catalyzed cascade reaction of N-H insertion and oxidative dehydrogenative aromatization: A new entry to 2-amino-phenols

A palladium-catalyzed cascade reaction of N-H insertion (NHI) and oxidative dehydrogenative aromatization (ODA) has been developed, which affords a straightforward and efficient way to access the carbazole precursors (2-arylamino-phenols) as well as to prepare 2-alkylamino-phenols from non-aromatic substrates. This journal is the Partner Organisations 2014.