41865-44-5

Usage

InChI:InChI=1/C17H18O2/c1-13-3-8-15(9-4-13)17(18)12-7-14-5-10-16(19-2)11-6-14/h3-6,8-11H,7,12H2,1-2H3

Upstream product

• 50990-40-4 (2E)-3-(4-methoxyphenyl)-1-(4-methylphenyl)prop-2-en-1-one 
• 122-00-9 para-methylacetophenone 
• 105-13-5 4-Methoxybenzyl alcohol 
• 67-56-1 methanol 
• 6552-66-5 3-(4-methoxyphenyl)-1-p-tolylprop-2-en-1-one 
• 109-77-3 malononitrile 
• 123-11-5 4-methoxy-benzaldehyde 
• 58824-48-9 1-(4-methylphenyl)-2-propen-1-ol 
• 5720-07-0 4-methoxyphenylboronic acid 
• 540800-70-2 3-(4-methoxyphenyl)-1-morpholinopropan-1-one 
• 2417-95-0 p-tolyllithium 
• 536-50-5 CH₃C₆H₄CH(CH₃)OH 
• 40122-37-0 1-(p-tolyl)cyclopropan-1-ol 
• 2393-23-9 4-methoxy-benzylamine 

Downstream Products

• 6552-66-5 3-(4-methoxyphenyl)-1-p-tolylprop-2-en-1-one 
• 102713-18-8 α-bromo-α,β-dihydro-4-methoxy-4'-methylchalcone 

Relevant academic research and scientific papers

Nickel-Catalyzed Selective Synthesis of α-Alkylated Ketones via Dehydrogenative Cross-Coupling of Primary and Secondary Alcohols

Herein, we describe an isolable, air-stable, homogeneous, nickel catalyst that performs dehydrogenative cross-coupling reaction between secondary and primary alcohols to result α-alkylated ketone products selectively. The sequence of steps involve in this one-pot reaction is dehydrogenation of both alcohols, condensation between the ketone and the aldehyde, and hydrogenation of the in situ-generated α,β-unsaturated ketone. Preliminary mechanistic investigation hints a radical mechanism following borrowing hydrogen reaction. (Figure presented.).

Scope and Mechanism of the Redox-Active 1,2-Benzoquinone Enabled Ruthenium-Catalyzed Deaminative α-Alkylation of Ketones with Amines

The catalytic system formed in situ from the reaction of a cationic Ru-H complex with 3,4,5,6-tetrachloro-1,2-benzoquinone was found to mediate a regioselective deaminative coupling reaction of ketones with amines to form the α-alkylated ketone products. Both benzylic and aliphatic primary amines were found to be suitable substrates for the coupling reaction with ketones in forming the α-alkylated ketone products. The coupling reaction of PhCOCD3 with 4-methoxybenzylamine showed an extensive H/D exchange on both α-CH2 (41% D) and β-CH2 (21%) positions on the alkylation product. The Hammett plot obtained from the reaction of acetophenone with para-substituted benzylamines p-X-C6H4CH2NH2 (X = OMe, Me, H, F, Cl, CF3) showed a strong promotional effect by the amine substrates with electron-releasing groups (ρ = -0.49 ± 0.1). The most significant carbon isotope effect was observed on the α-carbon of the alkylation product (Cα = 1.020) from the coupling reaction of acetophenone with 4-methoxybenzylamine. The kinetics of the alkylation reaction from an isolated imine substrate led to the empirical rate law: rate = k[Ru][imine]. A catalytically active Ru-catecholate complex was synthesized from the reaction of the cationic Ru-H complex with 3,5-di-tert-butyl-1,2-benzoquinone and PCy3. The DFT computational study was performed on the alkylation reaction, which revealed a stepwise mechanism of the [1,3]-carbon migration step via the formation of a Ru(IV)-alkyl species with a moderate energy of activation (ΔG? = 32-42 kcal/mol). A plausible mechanism of the catalytic alkylation reaction via an intramolecular [1,3]-alkyl migration of an Ru-enamine intermediate has been compiled on the basis of these experimental and computational data.

Designed pincer ligand supported Co(ii)-based catalysts for dehydrogenative activation of alcohols: Studies onN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines

Base-metal catalystsCo1,Co2andCo3were synthesized from designed pincer ligandsL1,L2andL3having NNN donor atoms respectively.Co1,Co2andCo3were characterized by IR, UV-Vis. and ESI-MS spectroscopic studies. Single crystal X-ray diffraction studies were investigated to authenticate the molecular structures ofCo1andCo3. CatalystsCo1,Co2andCo3were utilized to study the dehydrogenative activation of alcohols forN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines. Under optimized reaction conditions, a broad range of substrates including alcohols, anilines and ketones were exploited. A series of control experiments forN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines were examined to understand the reaction pathway. ESI-MS spectral studies were investigated to characterize cobalt-alkoxide and cobalt-hydride intermediates. Reduction of styrene by evolved hydrogen gas during the reaction was investigated to authenticate the dehydrogenative nature of the catalysts. Probable reaction pathways were proposed forN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines on the basis of control experiments and detection of reaction intermediates.

Ligand-tuned cobalt-containing coordination polymers and applications in water

Ligands play a key role in modern catalysis research and occasionally determine whether a reaction will take place under specific conditions, such as in water. In this experiment, ligands containing an indole-based diacid moiety were employed to prepare the corresponding cobalt coordination polymer material (Co-CIA) and porous oval polymer material (Co-NCIA). Interestingly, it was observed that Co-CIA could promote the alkylation of ketones with alcohols and alcohols with alcohols, while Co-NCIA was effective for the synthesis of 1-benzyl-2-aryl-1H-benzo[d]imidazoles from various phenylenediamine and benzyl alcohols through borrowing hydrogen and dehydrogenation strategies. Other mechanism explorations, such as deuterium labeling experiments and a kinetics study, were conducted to better understand Co-CIA and Co-NCIA systems and the related transformations. Our studies provided an efficient method for the development of highly active cobalt coordination polymer materials with excellent recovery performance for dehydrogenation and borrowing hydrogen reactions under water and base-free conditions.

Utility of Organoboron Reagents in Arylation of Cyclopropanols via Chelated Pd(II) Catalysis: Chemoselective Access to β-Aryl Ketones

Organoborane reagents were investigated as coupling partners to cyclopropanol-derived β-ketone enolates in the presence of a chelated Pd(II) catalyst. Efficient coupling of a range of electronically and sterically diverse cyclopropanols and aryl/alkenyl boronic derivatives (39 examples, 65-94% yield) could be achieved with the generation of synthetically important β-aryl ketone intermediates in a chemoselective fashion. This reactivity paradigm, which broadens the scope of aryl donor partners to homoenolates, allows open-flask conditions, water as a cosolvent, and preparation of halogen-bearing β-aryl ketones that are distinct from previous methods. This chelated Pd(II) catalysis appears to be different from the Pd(0) pathway, as evident from deuterium scrambling studies that could reveal differentiating protonolysis of an α-keto carbopalladium complex in the terminal step.

Monodisperse NiPd alloy nanoparticles decorated on mesoporous graphitic carbon nitride as a catalyst for the highly efficient chemoselective reduction of α,β-unsaturated ketone compounds

Herein, the study reported extraordinary chemoselective reduction with selectivity (>99%) by the catalytic transfer hydrogenation of various α,β-unsaturated ketones with a catalyst of NiPd alloy nanoparticles decorated on mesoporous graphitic carbon nitride (NiPd/mpg-C3N4) under mild conditions in a water/methanol medium. NiPd alloy NPs were synthesized by the reduction of metal salts in oleylamine (OAm) solution with the help of borane-tert-butylamine and then decorated on mpg-C3N4via a liquid phase self-assembly method. The NiPd/mpg-C3N4 nanocatalyst was characterized by TEM, XRD and ICP-MS. The NiPd/mpg-C3N4 nanocatalyst is a highly active catalyst for the chemoselective reduction of α,β-unsaturated ketones and all organic compounds were converted with high yield and 99% selectivity. In addition, the catalyst can be reused five times without an important loss in reaction yield. This journal is

Efficient Organoruthenium Catalysts for α-Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

A new family of phosphine free organometallic ruthenium(II) catalysts (Ru1–Ru4) supported by bidentate NN Schiff base ligands (L1–L4 where L1=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl) aniline, L2=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl)aniline, L3=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl)- aniline and L4=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl) aniline) was prepared and characterized. These half-sandwich complexes acted as catalysts for C?C bond formation and exhibited excellent performance in the dehydrogenative coupling of ketones and amides. In the synthesis of C–C bonds, alcohols were utilized as the alkylating agent. A broad range of substrates, including sterically hindered ketones and alcohols, were well tolerated under the optimized conditions (TON up to 47000 and TOF up to 11750 h?1). This ruthenium (II) catalysts were also active towards the dehydrogenative cyclization of o-amino benzyl alcohol for the formation of quinolines derivatives. Various polysubstituted quinolines were synthesized in moderate to excellent yields (TON up to 71000 and TOF up to 11830 h?1). Control experiments were carried out and the ruthenium hydride intermediate was characterized to support the reaction mechanism and a probable reaction pathway of dehydrogenative coupling for the C?C bond formation has been proposed.

Design and Synthesis of Zirconium-Containing Coordination Polymer Based on Unsymmetric Indolyl Dicarboxylic Acid and Catalytic Application on Borrowing Hydrogen Reaction

Catalytic borrowing hydrogen reaction is a very attractive transformation in the field of C-alkylation reaction. In this work, a new Zr (Zirconium)-containing coordination polymer containing unsymmetric indolyl dicarboxylic acid 1-(carboxymethyl)-1H-indole-5-carboxylic acid (H2CIA) was synthesized by the way of a solvothermal synthetic route and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Nitrogen adsorption-desorption, fourier transform infrared spectroscopy and X-ray photoelectronic spectroscopy (XPS). The coordination polymer Zr-CIA was employed as the catalyst for C-alkylation of acetophenone derivatives in the presence of benzyl alcohol. In addition, Zr-CIA catalyst was also observed to be effective in the reaction of alcohols with alcohols and high yields of alkylation products were achieved. Mechanism investigations were also conducted to better understand the catalysts and transformations. Meanwhile, the Zr-CIA could be reused at least five times without a notable decrease in activity and selectivity. (Figure presented.).

Microbial transformations of 4′-methylchalcones as an efficient method of obtaining novel alcohol and dihydrochalcone derivatives with antimicrobial activity

Biotransformations are an alternative method of receiving dihydrochalcones as a result of the reduction of α,β-unsaturated ketones-chalcones. In presented research, two strains of bacteria-Gordonia sp. DSM44456 and Rhodococcus sp. DSM364-were selected as

Phosphine-Free NNN-Manganese Complex Catalyzed α-Alkylation of Ketones with Primary Alcohols and Friedl?nder Quinoline Synthesis

Herein, we report a very simple and inexpensive catalytic system based on Earth's abundant transition metal manganese and on a bench-stable phosphine-free NNN-pincer ligand for an atom-efficient α-alkylations of ketones with primary alcohols via hydrogen-autotransfer C?C bond formation protocol. The precatalyst could be generated in situ and could be activated by using catalytic amount of base under milder conditions. A range of ketones were efficiently diversified with a broad range of primary alcohols in good to excellent isolated yields. Remarkably, this catalyst could also be employed for the synthesis of quinoline derivatives using 2-aminobenzyl alcohol as an alkylating agent. The later reaction is highly benign producing only hydrogen and water as byproducts. (Figure presented.).