22399-01-5

Upstream product

• 1122-91-4 4-bromo-benzaldehyde 
• 105-53-3 diethyl malonate 
• 685-87-0 Diethyl 2-bromomalonate 
• 95-76-1 m,p-dichloroaniline 
• 70146-78-0 diethyl 2-(4-bromobenzyl)malonate 
• 108-59-8 malonic acid dimethyl ester 

Downstream Products

• 99990-29-1 ethyl 3-(4-bromophenyl)-3-cyanopropanoate 
• 23270-30-6 <α-(O,O-Diethyl-phosphono)-4-brom-benzyl>-malonsaeure-diethylester 
• 70146-78-0 diethyl 2-(4-bromobenzyl)malonate 
• 77094-93-0 2-(4-bromophenyl)cyclopropane-1,1-dicarboxylic acid diethyl ester 
• 1312929-82-0 (2S,3R,4S)-4-ethyl 2-methyl 3-(4-bromophenyl)-5-oxopyrrolidine-2,4-dicarboxylate 
• 1312929-57-9 (2R,3S)-1,1-diethyl 3-methyl 2-(4-bromophenyl)-3-(diphenylmethyleneamino)propane-1,1,3-tricarboxylate 
• 1360814-47-6 diethyl 2-(1-(4-bromophenyl)-2-nitropropyl)malonate 

Relevant academic research and scientific papers

Ball-Milling-Enabled Reactivity of Manganese Metal**

Efforts to generate organomanganese reagents under ball-milling conditions have led to the serendipitous discovery that manganese metal can mediate the reductive dimerization of arylidene malonates. The newly uncovered process has been optimized and its mechanism explored using CV measurements, radical trapping experiments, EPR spectroscopy, and solution control reactions. This unique reactivity can also be translated to solution whereupon pre-milling of the manganese is required.

Co-Polymeric Nanosponges from Cellulose Biomass as Heterogeneous Catalysts for amine-catalyzed Organic Reactions

Heterogeneous catalysts prepared from biomass waste sources are attracting increasing interest. The reasons rely on the possibility of combining the virtuous approach of circular economy with the consolidated advantages of heterogeneous catalysis, namely the recycling of the system and the possibility to drive selectivity towards desired products. Herein we report a highly porous cellulose-based nanosponge (CNS) and its use as a recoverable catalyst for Henry and Knoevenagel reactions, two classical amino-catalyzed transformations. The material is obtained by cross-linking between TEMPO-oxidized cellulose nanofibers (TOCNF) and branched polyethyleneimine 25 kDa (bPEI) in the presence of citric acid. CNS have been developed as sorbent materials for water remediation but their use as heterogeneous catalysts was never investigated. The fully characterized micro- and nano-porous system guarantees a complete penetration of CNS, allowing reagents to diffuse within. Indeed, by modulating reaction conditions (catalyst loading, temperature, solvent, microwave versus conventional heating, relative ratio of reagents) it was possible to drive selectivity towards the desired products, while maintaining high efficiency in terms of conversion. The catalyst could be re-used several times without losing in catalytic efficiency. In most cases the products’ distribution is quite different from homogeneous conditions, this much more emphasizing the importance of this heterogeneous solution.

Programmed Sequential Additions to Halogenated Mucononitriles

Dihalomucononitriles were synthesized and their reactivity evaluated to assess their ability to function as linchpin reagents. Bis(2-chloroacrylonitrile) and bis(2-bromoacrylonitrile) were synthesized from 2,1,3-benzothiadiazole and undergo conjugate addition/elimination reactions with both nitrogen (40-95% yield) and carbon nucleophiles (72-93% yield). Secondary amines undergo monosubstitutions, while carbon nucleophiles are added twice. The sequence of addition of the nucleophiles could be controlled to give mixed addition products. The multicomponent coupling products could then be converted to natural product like motifs using intramolecular cyclization reactions.

Highly selective chromoionophores for ratiometric Na+ sensing based on an oligoethyleneglycol bridged bithiophene detection unit

Rapid and efficient measurement of sodium ion concentrations will benefit future studies and healthcare due to the importance of sodium to many biological processes. Ratiometric optical probes, where light absorption wavelengths shift according to ion con

Unnatural α-amino ethyl esters from diethyl malonate or ethyl β-bromo-α-hydroxyiminocarboxylate

We have explored here the scope of the age-old diethyl malonate-based accesses to α-amino esters involving Knoevenagel condensations of diethyl malonate on aldehydes, reductions of the resulting alkylidenemalonates, the preparation of the corresponding α-hydroxyimino esters and their final reduction. This synthetic pathway turned out to be general although some unexpected limitations were encountered. The synthetic modifications of some of the intermediates - using Suzuki-Miyaura coupling or cycloadditions - before undertaking the oximation step - provided accesses to further α-amino esters. Moreover, other pathways to α-hydroxyimino esters were explored including an attempt to improve the cycloadditions between ethyl β-bromo-α-hydroxyiminocarboxylate and various alkylfuranes.

Design and synthesis of 6-oxo-1,4,5,6-tetrahydropyrimidine-5-carboxylate derivatives as neuraminidase inhibitors

A series of 6-oxo-1,4,5,6-tetrahydropyrimidine-5-carboxylate derivatives were prepared to evaluate their ability of inhibiting neuraminidase (NA) of influenza A virus. All the compounds were synthesized in good yields starting from aldehyde by using a suitable synthetic strategy, which showed moderate inhibitory activity against influenza A NA. Compound 6g exhibited the strongest inhibitory activity against influenza virus A NA (IC50 = 17.64 μM), which indicated pyrimidine ring could be used as a core structure to design novel influenza NA inhibitors.

Asymmetric michael addition of N-tert-butanesulfinyl imidate with α,β-unsaturated diesters: Scope and application to the synthesis of indanone derivatives

An additive-free and highly diastereoselective Michael addition reaction of an N-tert-butanesulfinyl imidate to α,β-unsaturated diesters has been developed using LDA as a base with good to excellent yields. The utility of this chemistry is further demonstrated by the asymmetric synthesis of 3-substituted indanone derivatives 8a, 8d, 8e, and 8i with high enantiomeric excess, which are potential building blocks for preparing biologically active lead compounds.

Nickel(ii)-catalyzed enantioselective 1,3-dipolar cycloaddition of azomethine imines with alkylidene malonates

We demonstrated an asymmetric 1,3-dipolar cycloaddition of azomethine betaines with alkylidene malonates by using a chiral N,N'-dioxide- NiII complex as a catalyst. Both aromatic- and aliphatic-substituted alkylidene malonates were found to be suitable for the reaction. A range of transpyrazolone derivatives was exclusively obtained with excellent yields (up to 99% yield) and good enantioselectivities (up to 97% ee) under mild reaction conditions. The reaction could be carried out on a gram scale with the good results being maintained. Control experiments were performed to elucidate the specific diastereoselectivity of the reaction. The formation of single trans isomers was dominated by secondary orbital interactions between the ester groups of the dipolarophile and the azomethine imine. On the basis of the experimental results and previous reports, a possible catalytic model was assumed.

Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile

A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X ?-) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH?) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure Ci - 'C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure Ci - 'C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X?-) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

Chiral-Zn(NTf2)2-complex-catalyzed diastereo- and enantioselective direct conjugate addition of arylacetonitriles to alkylidene malonates

Chiral N,N′-dioxide/Zn(NTf2)2 complexes were demonstrated to be highly effective in the direct asymmetric conjugate addition of arylacetonitriles to alkylidene malonates under mild conditions. A wide range of substrates were tolerated to afford their corresponding products in moderate-to-good yields with high diastereoselectivities (82:18->99:1 d.r.) and enantioselectivities (81-99 % ee). The reactions performed well, owing to the high Lewis acidity of the metal triflimidate and a ligand-acceleration effect. The N,N′-dioxide also benefited the deprotonation process as a Bronsted base. The catalytic reaction could be performed on the gram-scale with retention of yield, diastereoselectivity, and enantioselectivity. The products that contained functional groups were ready for further manipulation. In addition, a possible catalytic model was proposed to explain the origin of the asymmetric induction. Copyright