52927-44-3

Upstream product

• 67-56-1 methanol 
• 6773-29-1 dimethyl diazomalonate 
• 104-88-1 4-chlorobenzaldehyde 
• 108-59-8 malonic acid dimethyl ester 
• 32884-52-9 1-(4-{[(4-chlorophenyl)methylene]amino}phenyl)ethanone 
• 142918-00-1 3-(4-Chloro-phenyl)-2-methyl-5-oxo-isoxazolidine-4-carboxylic acid methyl ester 

Downstream Products

• 74-96-4 ethyl bromide 
• 86661-24-7 2-[(R)-(4-Chloro-phenyl)-((S)-2-oxo-cyclohexyl)-methyl]-malonic acid dimethyl ester 
• 86661-24-7 2-[(2-oxocyclohexyl)-4-chlorophenylmethyl]malonic acid dimethyl ester 
• 86661-24-7 (-)-(1'S,1''S)-<(4-Chlorphenyl)(2-oxocyclohexyl)methyl>propandisaeure-dimethylester 
• 696627-55-1 2-[2-(4-bromo-benzoyl)-1-(4-chloro-phenyl)-butyl]-malonic acid dimethyl ester 
• 1111239-70-3 dimethyl 2-((1R,2R)-1-(4-chlorophenyl)-2-methyl-3-oxopropyl)malonate 
• 1030919-31-3 dimethyl 2-((Z)-2-benzylidene-1-(4-chlorophenyl)-3-oxobutyl)propanedioate 
• 1116152-87-4 (R)-dimethyl 2-[1-(4-chlorophenyl)-2-(furan-2-yl)-2-oxoethyl]malonate 

Relevant academic research and scientific papers

Catalysis with inorganic cations. VII. The catalytic process of the Diels-Alder reaction with magnesium perchlorate in CH2Cl2: Kinetic investigation and spectroscopic detection of the complexed intermediate

The 2-arylidene-malonic acid dimethyl ester is a dienophile suitable to be coordinated by Mg(II). The formation of the dienophile/cation complex in a ratio 2:1 in a non-coordinating solvent has been demonstrated by NMR spectroscopy. Kinetic determinations performed in dichloromethane evidenced the high reactivity of the system. The high affinity for Mg(II) of the reacting dienophile allows the reaction to be performed under catalytic conditions, whose single steps have been clarified by both spectroscopic and kinetic methods.

Catalysis with inorganic cations. VIII. Macrocyclic-yliden malonates: Synthesis, spectroscopic investigation, and metal perchlorate catalysis of the Diels-Alder reaction

Macrocyclic-yliden malonates 8-10 have been prepared by Knoevenagel condensation of differently sized crown malonates 5-7 with several aldehydes. The spectroscopic investigations of derivatives 8-10a in several solvents (acetone, acetonitrile, and dichlor

A novel sublimable organic salt: Synthesis, characterization, thermal behavior, and catalytic activity for the synthesis of arylidene, heteroarylidene, and alkylidene malonates

A novel sublimable organic salt was synthesized, and its chemical structure was characterized by FTIR, 1D NMR, 2D NMR, and elemental analysis. In addition, the thermal phase transitions and thermal stability of new organic salt were investigated. The DSC and TGA results showed that the organic salt could convert into constituent molecules at dec. ~ 200?°C) under atmospheric pressure without forming the liquid phase. Then, it was recondensed to regenerate the initial organic salt in the cool part of the vial. Therefore, it can be a promising organic salt towards the regeneration of spent catalyst from synthesis processes when the reaction mixture contains poorly volatile components and includes its use in gas-phase procedures. Also, the catalytic efficiency of new organic salt was investigated in the Knoevenagel condensation reaction. A variety of substituted arylidene and alkylidene malonates were isolated in 78–95% yield within six hours.? Under the optimized reaction conditions, the current catalytic procedure exhibited superiority compared to the mixed piperazine/acetic acid, piperidine/acetic acid, and piperidinium acetate. There were no significant changes in the new organic salt chemical structure and catalytic activity even after the 5th run. This work revealed the importance of the existence of simultaneous hydrogen bond acceptor/donor groups in our environmentally friendly catalyst to promote the Knoevenagel condensation reaction without the use of metal-containing catalysts.

Solid-phase synthesis of arylidene and alkylidene malonates, as versatile intermediates, catalyzed using mesoporous poly-melamine–formaldehyde as a nitrogen-rich porous organic polymer (POP)

An efficient solid/slurry-state synthesis of arylidene and alkylidene malonates as versatile intermediates is developed in the presence of mesoporous poly-melamine–formaldehyde. The condensation reaction was conducted through a ball milling process as a non-conventional procedure and a greener methodology at room temperature under solvent-free conditions. The mesoporous heterogeneous catalyst could be recovered and reused ten times, and the results showed a negligible loss of catalytic activity. Various aryl- and heteroarylidene malonates, as well as dimethyl (cyclohexylidene)malonate, were isolated in good to high yields under optimal conditions. The use of hazardous reagents and solvents were minimized in the current method, and separation of catalyst and products, as well as the recovery and reusing of catalyst, were performed by cost-effective procedures. This work revealed that the synergistic effect of numerous Lewis base sites together with acceptor-donner hydrogen bonding functional groups in porous organic polymer (POP), and its high porosity plays a vital role to promote the carbon–carbon coupling reaction in the solid phase synthesis.

Reductive Knoevenagel Condensation with the Zn-AcOH System

An efficient gram-scale one-pot approach to 2-substituted malonates and related structures is developed, starting from commercially available aldehydes and active methylene compounds. The technique combines Knoevenagel condensation with the reduction of the C=C bond in the resulting activated alkenes with the Zn-AcOH system. The relative ease with which the C=C bond reduction occurs can be traced to the accepting abilities of the substituents in the intermediate arylidene malonates.

Asymmetric catalytic [4+3] cycloaddition ofortho-quinone methides with oxiranes

Catalytic enantioselective [4+3] cycloaddition reaction betweeno-quinone methides and oxiranes was achieved by using a chiralN,N′-dioxide/TbIIIcomplex as the catalyst, affording medium-sized hydrodioxepine derivatives in high yields (up to 99%)

Cross-linked polystyrene-TiCl4 complex as a reusable Lewis acid catalyst for solvent-free Knoevenagel condensations of 1,3-dicarbonyl compounds with aldehydes

Cross-linked polystyrene copolymer beads with the average particle size in the range of (50–80 mesh size) were prepared by a new method, characterized and functionalized with titanium tetrachloride to afford the corresponding polystyrene?titanium tetrachloride complex in one step reaction and characterized by FT-IR, UV, TGA, DSC, XRD, SEM, BET. This polymer metal complex (PS/TiCl4) was used as a heterogeneous, recoverable, reusable Lewis acid for solvent-free Knoevenagel condensations of 1,3-diketones with aromatic aldehydes under green and mild conditions. The rate of reactions was found to decrease with an increasing percentage of crosslinking and the mesh size of the copolymer beads. This complex showed good stability and catalytic activity in the Knoevenagel reactions.

Stereospecific copper(II)-catalyzed tandem ring opening/oxidative alkylation of donor-acceptor cyclopropanes with hydrazones: Synthesis of tetrahydropyridazines

Aerobic copper(II)-catalyzed tandem ring opening and oxidative C-H alkylation of donor-acceptor cyclopropanes with bisaryl hydrazones is accomplished to produce tetrahydropyridazines, in which copper(II) plays dual role as a Lewis acid as well as redox catalyst. The reaction is stereospecific, and optically active cyclopropanes can be reacted with high optical purities (89-98% enantiomeric excess). The substrate scope, functional group tolerance, dual role of the copper(II) catalyst, and the use of air as an oxidant are the important practical features. A product bearing a 3-bromoaryl group can be subjected to Pd-catalyzed Suzuki coupling with boronic acid in high yield.

An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)3-Catalyzed [3+2] Cycloaddition of Donor–Acceptor Cyclopropanes with Thionoesters

A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf)3-promoted [3+2] cycloaddition of donor–acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.

Nucleophilic Ring Opening of Donor-Acceptor Cyclopropanes Catalyzed by a Br?nsted Acid in Hexafluoroisopropanol

A general, Br?nsted acid catalyzed method for the room temperature, nucleophilic ring opening of donor-acceptor cyclopropanes in fluorinated alcohol solvent, HFIP, is described. Salient features of this method include an expanded cyclopropane scope, including those bearing single keto-acceptor groups and those bearing electron-deficient aryl groups. Notably, the catalytic system proved amenable to a wide range of nucleophiles including arenes, indoles, azides, diketones, and alcohols.