20099-89-2

Usage

Uses

Used in Pharmaceutical Industry:
4-CYANOPHENACYL BROMIDE is used as an intermediate in the synthesis of novel Glycogen synthase kinase 3 (GSK-3) inhibitors for the irreversible inhibitory activity of GSK-3. This makes it a valuable compound in the development of new drugs targeting GSK-3 related diseases.
Used in Chemical Synthesis:
4-CYANOPHENACYL BROMIDE is used as a key building block in the synthesis of various organic compounds, such as 3-acylindolizines, (2R,3R)-3-[4-(4-cyanophenyl)thiazol-2-yl]-2-(2,4-difluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-2-butanol, and 1-[2-(4-cyanophenyl)-2-oxoethyl]-1,10-phenanthrolinium bromide. These synthesized compounds have potential applications in various fields, including pharmaceuticals, agrochemicals, and materials science.

InChI:InChI=1/C10H7BrO/c1-2-8-3-5-9(6-4-8)10(12)7-11/h1,3-6H,7H2

Upstream product

• 1443-80-7 4-cyanophenyl methyl ketone 
• 25309-65-3 4-ethylbenzonitrile 
• 67-56-1 methanol 
• 157729-39-0 4-(2-bromoethynyl)-benzonitrile 
• 100-47-0 benzonitrile 
• 598-21-0 2-Bromoacetyl bromide 
• 3435-51-6 4-ethenylbenzonitrile 
• 105-07-7 4-cyanobenzaldehyde 

Downstream Products

• 103962-24-9 4-(2-[1,2,4]triazol-1-ylacetyl)benzonitrile 
• 138470-03-8 6-<5-<2-(4-Cyanphenacyloxy)-phenyl>-1,2,4-dithiazol-3-yliden>-2,4-cyclohexadien-1-on 
• 13367-81-2 10-methylacridinium cation 
• 1443-80-7 4-cyanophenyl methyl ketone 
• 101219-69-6 4-(1-hydroxyethyl)benzonitrile 
• 85554-13-8 (±)-4-(2-bromo-1-hydroxyethyl)benzonitrile 
• 3490-50-4 2-diazo-1-(4-cyanophenyl)ethanone 
• 182760-06-1 ravuconazole 
• 69039-63-0 2-(4-cyano-phenyl)-2-oxo-ethyl 

Relevant academic research and scientific papers

Unexpected ritter reaction during acid-promoted 1,3-dithiol-2-one formation

A series of aryl-substituted 1,3-dithiol-2-ones was prepared by the Bhattacharya-Hortmann cyclization method. Unexpectedly, a Ritter reaction occurred during the acid-catalyzed cyclization at the cyano group of the aryl substituents and 1,3-dithiol-2-ones bearing a carboxy or a carboxamide group could be selectively obtained (see 1 and 2a in Scheme 1). The formation of the acid or the amide functionality was temperature-dependent so that the one or the other group could be introduced selectively by modifying the reaction temperature. Copyright

Electroselective α-bromination of acetophenone using: In situ bromonium ions from ammonium bromide

A greener and expeditious method for the side chain bromination of acetophenone using in situ generated bromonium ions from NH4Br and a catalytic amount of H2SO4 as a supporting electrolyte in a H2O:CH3CN medium at ambient temperature has been developed in an undivided cell equipped with a Pt/Pt electrode. This method results in a good yield (80%) of α-bromo acetophenone with high selectivity when only 2F of electricity was passed. Optimization studies such as variation of the current density, charge passed, solvent, solvent/water ratio, acid, acid strength, bromide salt, bromide salt concentration, etc., are carried out and reported.

High Chemo-/Stereoselectivity for Synthesis of Polysubstituted Monofluorinated Pyrimidyl Enol Ether Derivatives

A novel intramolecular Smiles rearrangement of α-fluoro-β-keto-pyrimidylsulfones (usually used as a carbon nucleophile) was developed, providing a versatile avenue for synthesis of tri/tetra-substituted monofluorinated pyrimidyl enol ethers. Among these, diverse (Z)-monofluorovinylsulfones and sulfinates were efficiently assembled by adding extra electrophile and fine-tuning reaction conditions. The process is triggered by a keto-enol tautomerism from enol oxyanion to pyrimidine 2-carbon, completely different from the classical carbon nucleophilic addition reaction approach.

Base-Catalyzed Intramolecular Defluorination/O-Arylation Reaction for the Synthesis of 3-Fluoro-1,4-oxathiine 4,4-Dioxide

A novel process involving base-catalyzed intramolecular defluorination/O-arylation of readily available α-fluoro-β-one-sulfones was realized and provided a series of 3-fluoro-1,4-oxathiine 4,4-dioxide derivatives in good to excellent yields. Unlike traditional defluorination reactions with stoichiometric base as the deacid reagent, this process is triggered by a catalytic amount of base (TMG: tetramethylguanidine) and molecular sieves serve as both an adsorbent to remove HF acid and an activator to assist C-F bond cleavage.

An umpolung oxa-[2,3] sigmatropic rearrangement employing arynes for the synthesis of functionalized enol ethers

An oxa-[2,3] sigmatropic rearrangement involving arynes is reported featuring the umpolung of ketones, where the C=O bond polarity is reversed. The in situ-generated sulfur ylides from β-keto thioethers and arynes undergo efficient rearrangement allowing the facile and robust synthesis of functionalized enol ethers in high yields and excellent functional group compatibility. Preliminary mechanistic studies rule out the possibility of Pummerer-type rearrangement operating in this case.

Flexible on-site halogenation paired with hydrogenation using halide electrolysis

Direct electrochemical halogenation has appeared as an appealing approach in synthesizing organic halides in which inexpensive inorganic halide sources are employed and electrical power is the sole driving force. However, the intrinsic characteristics of direct electrochemical halogenation limit its reaction scope. Herein, we report an on-site halogenation strategy utilizing halogen gas produced from halide electrolysis while the halogenation reaction takes place in a reactor spatially isolated from the electrochemical cell. Such a flexible approach is able to successfully halogenate substrates bearing oxidatively labile functionalities, which are challenging for direct electrochemical halogenation. In addition, low-polar organic solvents, redox-active metal catalysts, and variable temperature conditions, inconvenient for direct electrochemical reactions, could be readily employed for our on-site halogenation. Hence, a wide range of substrates including arenes, heteroarenes, alkenes, alkynes, and ketones all exhibit excellent halogenation yields. Moreover, the simultaneously generated H2at the cathode during halide electrolysis can also be utilized for on-site hydrogenation. Such a strategy of paired halogenation/hydrogenation maximizes the atom economy and energy efficiency of halide electrolysis. Taking advantage of the on-site production of halogen and H2gases using portable halide electrolysis but not being suffered from electrolyte separation and restricted reaction conditions, our approach of flexible halogenation coupled with hydrogenation enables green and scalable synthesis of organic halides and value-added products.

Oxidation Potential-Guided Electrochemical Radical-Radical Cross-Coupling Approaches to 3-Sulfonylated Imidazopyridines and Indolizines

Oxidation potential-guided electrochemical radical-radical cross-coupling reactions between N-heteroarenes and sodium sulfinates have been established. Thus, simple cyclic voltammetry measurement of substrates predicts the likelihood of successful radical-radical coupling reactions, allowing the simple and direct synthetic access to 3-sulfonylated imidazopyridines and indolizines. The developed electrochemical radical-radical cross-coupling reactions to sulfonylated N-heteroarenes boast the green synthetic nature of the reactions that are oxidant- and metal-free.

Ground-State Electron Transfer as an Initiation Mechanism for Biocatalytic C-C Bond Forming Reactions

The development of non-natural reaction mechanisms is an attractive strategy for expanding the synthetic capabilities of substrate promiscuous enzymes. Here, we report an "ene"-reductase catalyzed asymmetric hydroalkylation of olefins using α-bromoketones as radical precursors. Radical initiation occurs via ground-state electron transfer from the flavin cofactor located within the enzyme active site, an underrepresented mechanism in flavin biocatalysis. Four rounds of site saturation mutagenesis were used to access a variant of the "ene"-reductase nicotinamide-dependent cyclohexanone reductase (NCR) from Zymomonas mobiles capable of catalyzing a cyclization to furnish β-chiral cyclopentanones with high levels of enantioselectivity. Additionally, wild-type NCR can catalyze intermolecular couplings with precise stereochemical control over the radical termination step. This report highlights the utility for ground-state electron transfers to enable non-natural biocatalytic C-C bond forming reactions.

Rhodium-Catalyzed Annulation of Phenacyl Ammonium Salts with Propargylic Alcohols via a Sequential Dual C-H and a C-C Bond Activation: Modular Entry to Diverse Isochromenones

Given their omnipresence in natural products and pharmaceuticals, isochromenone congeners are one of the most privileged scaffolds to synthetic chemists. Disclosed herein is a dual (ortho/meta) C-H and C-C activation of phenacyl ammonium salts (acylammonium as traceless directing group) toward annulation with propargylic alcohols to accomplish rapid access for novel isochromenones by means of rhodium catalysis from readily available starting materials. This operationally simple protocol features broad substrate scope and wide functional group tolerance. Importantly, the protocol circumvents the need of any stoichiometric metal oxidants and proceeds under aerobic conditions.

Usnic Acid Enaminone-Coupled 1,2,3-Triazoles as Antibacterial and Antitubercular Agents

(+)-Usnic acid, a product of secondary metabolism in lichens, has displayed a broad range of biological properties such as antitumor, antimicrobial, antiviral, anti-inflammatory, and insecticidal activities. Interested by these pharmacological activities and to tap into its potential, we herein present the synthesis and biological evaluation of new usnic acid enaminone-conjugated 1,2,3-triazoles 10-44 as antimycobacterial agents. (+)-Usnic acid was condensed with propargyl amine to give usnic acid enaminone 8 with a terminal ethynyl moiety. It was further reacted with various azides A1-A35 under copper catalysis to give triazoles 10-44 in good yields. Among the synthesized compounds, saccharin derivative 36 proved to be the most active analogue, inhibiting Mycobacterium tuberculosis (Mtb) at an MIC value of 2.5 μM. Analogues 16 and 27, with 3,4-difluorophenacyl and 2-acylnaphthalene units, respectively, inhibited Mtb at MIC values of 5.4 and 5.3 μM, respectively. Among the tested Gram-positive and Gram-negative bacteria, the new derivatives were active on Bacillus subtilis, with compounds 18 [3-(trifluoromethyl)phenacyl] and 29 (N-acylmorpholinyl) showing inhibitory concentrations of 41 and 90.7 μM, respectively, while they were inactive on the other tested bacterial strains. Overall, the study presented here is useful for converting natural (+)-usnic acid into antitubercular and antibacterial agents via incorporation of enaminone and 1,2,3-triazole functionalities.