2583-25-7

Usage

Uses

Used in Pharmaceutical Production:
Allylmalonic acid is used as an intermediate in the synthesis of pharmaceuticals for its ability to form carbon-carbon bonds and act as a precursor to other organic compounds, contributing to the development of new drugs.
Used in Dye Manufacturing:
In the dye industry, allylmalonic acid is used as a component in the production of dyes, where its chemical properties are leveraged to create a range of colorants for various applications.
Used in Adhesive Formulation:
Allylmalonic acid is used as a component in certain adhesive formulations, enhancing their performance and bonding capabilities.
Used in Organic Synthesis:
As a Michael acceptor, allylmalonic acid is used in organic synthesis for the formation of carbon-carbon bonds, which is crucial in creating a variety of organic compounds.
Safety Considerations:
Allylmalonic acid is considered a hazardous substance, necessitating careful handling and storage to ensure safety in its applications and during its production processes.

InChI:InChI=1/C6H8O4/c1-2-3-4(5(7)8)6(9)10/h2,4H,1,3H2,(H,7,8)(H,9,10)/p-2

Upstream product

• 556-56-9 allyl iodid 
• 996-82-7 sodium diethylmalonate 
• 17920-23-9 diethyl propargylmalonate 
• 64-17-5 ethanol 
• 40637-56-7 dimethyl allylmalonate 
• 113427-02-4 2,2-dimethyl-5-(prop-2-en-1-yl)-1,3-dioxane-4,6-dione 
• 2565-43-7 5-allyl-pyrimidine-2,4,6-trione 
• 106-95-6 allyl bromide 
• 2049-80-1 (2-propenyl)propanedioic acid diethyl ester 

Downstream Products

• 100797-66-8 2-((E)-2-methoxy-benzylidene)-pent-4-enoic acid 
• 2049-80-1 (2-propenyl)propanedioic acid diethyl ester 
• 591-80-0 pent-4-enoic acid 
• 15719-64-9 methylammonium carbonate 
• 103647-45-6 2-((E)-3-nitro-benzylidene)-pent-4-enoic acid 
• 1144-90-7 5-allyl-2-phenyl-[1,3]oxazine-4,6-dione 
• 56239-07-7 4-acetamido-5-phenylpyrimidine 
• 109113-93-1 2,6-dihydroxy-3-allyl-4-oxo-9-phenylpyrimido<1,6-a>pyrimidine 
• 109113-90-8 4-oxo-3-allyl-2-acetoxy-9-phenylpyrimido<1,6-a>pyrimidine 
• 600-05-5 2,3-dibromopropionic acid 
• 343926-87-4 2,4-Dibromo-pentanoic acid 
• 93059-33-7 α-(2-Chlorobenzylidene)-γ-methyl-γ-butyrolactone 
• 1308663-00-4 C₁₂H₁₂O₃S 
• 1323421-53-9 S-tert-butyl (S)-2-((S)-(4-chlorophenyl)(4-methylphenylsulfonamido)methyl)pent-4-enethioate 

Relevant academic research and scientific papers

Predicted incorporation of non-native substrates by a polyketide synthase yields bioactive natural product derivatives

The polyether ionophore monensin is biosynthesized by a polyketide synthase that delivers a mixture of monensins A and B by the incorporation of ethyl- or methyl-malonyl-CoA at its fifth module. Here we present the first computational model of the fifth acyltransferase domain (AT5mon) of this polyketide synthase, thus affording an investigation of the basis of the relaxed specificity in AT5mon, insights into the activation for the nucleophilic attack on the substrate, and prediction of the incorporation of synthetic malonic acid building blocks by this enzyme. Our predictions are supported by experimental studies, including the isolation of a predicted derivative of the monensin precursor premonensin. The incorporation of non-native building blocks was found to alter the ratio of premonensins A and B. The bioactivity of the natural product derivatives was investigated and revealed binding to prenyl-binding protein. We thus show the potential of engineered biosynthetic polyketides as a source of ligands for biological macromolecules. PKS analysis: Which substrate is incorporated, how does it happen and what is produced? Computational modeling of the fifth acyltransferase domain of a polyketide synthase predicts that the enzyme incorporates non-native building blocks into the polyether ionophore monensin to give natural product derivatives with biological activity.

Design and synthesis of malonamide derivatives as antibiotics against methicillin-resistant staphylococcus aureus

Methicillin-resistant Staphylococcus aureus (MRSA) is a serious threat to humans. Most existing antimicrobial drugs, including the β-lactam and quinoxiline classes, are not effective against MRSA. In this study, we synthesized 24 derivatives of malonamide, a new class of antibacterial agents and potentiators of classic antimicrobials. A derivative that increases bacterial killing and biofilm eradication with low cell toxicity was created.

Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)

The use of mono-substituted malonic acid half oxyesters (SMAHOs) has been hampered by the sporadic references describing their preparation. An evaluation of different approaches has been achieved, allowing to define the best strategies to introduce diversity on both the malonic position and the ester function. A classical alkylation step of a malonate by an alkyl halide followed by a monosaponification gave access to reagents bearing different substituents at the malonic position, including functionalized derivatives. On the other hand, the development of a monoesterification step of a substituted malonic acid derivative proved to be the best entry for diversity at the ester function, rather than the use of an intermediate Meldrum acid. Both these transformations are characterized by their simplicity and efficiency, allowing a straightforward access to SMAHOs from cheap starting materials.

Catalytic Generation of Rhodium Silylenoid for Alkene-Alkyne-Silylene [2 + 2 + 1] Cycloaddition

An alkene-alkyne-silylene [2 + 2 + 1] cycloaddition takes place in the rhodium-catalyzed reaction of 1,6-enynes with borylsilanes bearing an alkoxy group on the silicon atoms, which react as synthetic equivalents of silylene. The reaction proceeds efficiently in 1,2-dichloroethane at 80-110 °C in the presence of a rhodium catalyst bearing bis(diphenylphosphino)methane (DPPM) as a ligand to afford 1-silacyclopent-2-enes in good to high yields.

Exploring the Promiscuous Enzymatic Activation of Unnatural Polyketide Extender Units in Vitro and in Vivo for Monensin Biosynthesis

The incorporation of new-to-nature extender units into polyketide synthesis is an important source for diversity yet is restricted by limited availability of suitably activated building blocks in vivo. We here describe a straightforward workflow for the biogenic activation of commercially available new-to-nature extender units. Firstly, the substrate scope of a highly flexible malonyl co-enzyme A synthetase from Streptomyces cinnamonensis was characterized. The results were matched by in vivo experiments in which the said extender units were accepted by both the polyketide synthase and the accessory enzymes of the monensin biosynthetic pathway. The experiments gave rise to a series of predictable monensin derivatives by the exploitation of the innate substrate promiscuity of an acyltransferase and downstream enzyme functions.

Electrochemistry-Enabled Ir-Catalyzed Vinylic C-H Functionalization

Synergistic use of electrochemistry and organometallic catalysis has emerged as a powerful tool for site-selective C-H functionalization, yet this type of transformation has thus far mainly been limited to arene C-H functionalization. Herein, we report the development of electrochemical vinylic C-H functionalization of acrylic acids with alkynes. In this reaction an iridium catalyst enables C-H/O-H functionalization for alkyne annulation, affording α-pyrones with good to excellent yields in an undivided cell. Preliminary mechanistic studies show that anodic oxidation is crucial for releasing the product and regeneration of an Ir(III) intermediate from a diene-Ir(I) complex, which is a coordinatively saturated, 18-electron complex. Importantly, common chemical oxidants such as Ag(I) or Cu(II) did not give significant amounts of the desired product in the absence of electrical current under otherwise identical conditions.

Bifunctional Iminophosphorane Catalyzed Enantioselective Sulfa-Michael Addition to Unactivated α-Substituted Acrylate Esters

The highly enantioselective sulfa-Michael addition of alkyl thiols to unactivated α-substituted acrylate esters catalyzed by a bifunctional iminophosphorane organocatalyst under mild conditions is described. The strong Br?nsted basicity of the iminophosphorane moiety of the catalyst provides the necessary activation of the alkyl thiol pro-nucleophile, while the two tert-leucine residues flanking a central thiourea hydrogen-bond donor facilitate high enantiofacial selectivity in the protonation of the transient enolate intermediate. The reaction is broad in scope with respect to the alkyl thiol, the ester moiety, and the α-substituent of the α,β-unsaturated ester, affords sulfa-Michael adducts in excellent yields (up to >99%) and enantioselectivities (up to 96% ee), and is amenable to decagram scale-up using catalyst loadings as low as 0.05 mol %.

Microwave-assisted synthesis of furo[3,2-c]-1,8-naphthyridines

Microwave-assisted ring-conversion reactions of some pyrido[1,2-a] pyrimidine derivatives to 1,8-naphthyridines have been investigated. Novel furo[3,2-c]-1,8-naphthyridine compounds were synthesized in good yields under thermal reaction conditions. Both microwave and classical heating methods have been found to be satisfactory for the synthesis of new 1,8-naphthyridines.

Expanding the utility of Bronsted base catalysis: Biomimetic enantioselective decarboxylative reactions

As a result of the low reactivity of simple esters, the use of them as nucleophiles in direct asymmetric transformations is a long-standing challenge in synthetic organic chemistry. Nature approaches this difficulty through a decarboxylative mechanism, which is used for polyketide synthesis. Inspired by nature, we report guanidine-catalyzed biomimetic decarboxylative C-C and C-N bond-formation reactions. These highly enantioselective decarboxylative Mannich and amination reactions utilized malonic acid half thioesters as simple ester surrogates. It is proposed that nucleophilic addition precedes decarboxylation in the mechanism, which has been investigated in detail through the identification of intermediates by using electrospray ionization (ESI) mass-spectrometric analysis and DFT calculations. Copyright

Catalytic asymmetric protonation of chiral calcium enolates via 1,4-addition of malonates

Catalytic asymmetric protonation of chiral calcium enolates was performed. Chiral calcium enolates, prepared in situ from imides and malonates via 1,4-addition in the presence of catalytic amounts of Ca(OEt)2, Ph-PyBox, and achiral phenol, were smoothly protonated to afford adducts bearing tertiary asymmetric carbons in high yields with high enantioselectivities. The adducts were readily converted to optically active 2-substituted 1,5-dicarboxylic acid derivatives.