27730-03-6

Usage

Synthesis Reference(s)

Journal of the American Chemical Society, 77, p. 590, 1955 DOI: 10.1021/ja01608a021Tetrahedron Letters, 26, p. 2471, 1985 DOI: 10.1016/S0040-4039(00)94856-1

InChI:InChI=1/C15H11NO4/c17-13(10-4-2-1-3-5-10)15-14(20-15)11-6-8-12(9-7-11)16(18)19/h1-9,14-15H

Upstream product

• 555-16-8 4-nitrobenzaldehdye 
• 1222-98-6 4-nitrochalcone 
• 98-86-2 acetophenone 
• 100-42-5 styrene 
• 70-11-1 α-bromoacetophenone 
• 124-38-9 carbon dioxide 
• 532-27-4 1-chloroacetophenone 
• 2960-55-6 (E)-3-(4-nitrophenyl)-1-phenylprop-2-en-1-one 

Downstream Products

• 93850-85-2 [(4S,5R)-2,2-Dimethyl-5-(4-nitro-phenyl)-[1,3]dioxolan-4-yl]-phenyl-methanone 

Relevant academic research and scientific papers

Synthesis and characterization of 1,3,5-triarylpyrazol-4-ols and 3,5-diarylisoxazol-4-ols from chalcones and theoretical studies of the stability of pyrazol-4-ol toward acid dehydration

The synthesis of diverse pyrazol-4-ol and isoxazole-4-ol heterocycles involving only 3 reaction steps is reported in this study. However, the synthesis of carboxamide pyrazol-4-ol has failed in the conditions used in the synthesis, acid methanol solution. The carboxamide pyrazol-4-ol decomposes via dehydration, forming the respective pyrazol. Theoretical calculations were used to elucidate the dehydration reaction. We have found a mechanism for acid-catalyzed dehydration that can explain the experimental observations. The calculated free energy profile for acid-catalyzed dehydration of the carboxamide pyrazol-4-ol and phenylpyrazole-4-ol point out that the latter is more stable in relation dehydration, with a dehydration rate 100 times smaller in acid methanol solution.

Application of chiral TADDOL ligand and rare earth metal amide in combined catalysis of asymmetric reaction

The invention relates to application of chiral TADDOL ligand and rare earth metal amide in combined catalysis of asymmetric epoxidation reaction of chalcone compounds. According to the application, alpha, beta-unsaturated ketone shown in a formula (1) and tert-butyl hydroperoxide react in the presence of organic alkali under the combined catalytic action of a chiral TADDOL ligand shown in a formula (3) and rare earth metal amide in an anhydrous, oxygen-free and protective atmosphere to obtain the chiral epoxy compound shown in the formula (2) after the reaction is completed, wherein R1 is selected from hydrogen, alkyl, halogen, alkoxy, trifluoromethyl, nitro or cyano, R2 is selected from phenyl, substituted phenyl, naphthyl, furyl or thienyl; R3 and R4 are respectively and independently selected from alkyl, phenyl or R3 and R4 and carbon atoms connected with R3 and R4 form naphthenic base; Ar is phenyl, substituted phenyl, biphenyl or naphthyl; the molecular formula of the rare earth metal amide is RE [N (SiMe3) 2] 3. The method has the advantages of wide substrate application range, high yield and high enantioselectivity.

N-Heterocyclic Carbene Catalyzed Oxidative Coupling of Alkenes/ α-Bromoacetophenones with Aldehydes: A Facile Entry to α,β-Epoxy Ketones

A novel, N-heterocyclic carbene (NHC) catalyzed direct oxidative coupling of styrenes with aldehydes has been described for the synthesis of α,β-epoxy ketones in good yields. This unprecedented regioselective oxidative coupling employs NBS/DBU/DMSO (DBU=1,8-diazabicyclo [5.4. 0] undec-7-ene, DMSO=dimethylsulfoxide, NBS=N-bromosuccinimide) as an oxidative system at ambient conditions. Additionally, first NHC-catalyzed Darzens reaction of α-bromoketones and aldehydes under mild reaction conditions has also been described. Interestingly, mechanistic studies have revealed the preferred reactivity of NHC with alkene/α-bromoketone rather than aldehydes, thus proceeding via the ketodeoxy Breslow intermediate.

Darzens reaction rate enhancement using aqueous media leading to a high level of kinetically controlled diastereoselective synthesis of steroidal epoxyketones

Darzens reactions between halocarbonyls and aldehydes have been carried out in water in the presence of a Li+-containing base, a phase-transfer catalyst, and granular polytetrafluoroethylene under mechanical stirring. Reactions using both aromatic and aliphatic aldehydes produced epoxides stereoselectively in good to excellent yields. This is the first time that aliphatic aldehydes with α-H have been used in aqueous Darzens reactions. The Darzens reactions were much faster in water than in organic solvents. This aqueous rate enhancement occurred for Darzens reactions between enantiopure steroidal haloketones and aldehydes, yielding enantiopure spiroepoxides with a high level of kinetically controlled diastereoselectivity. Chromatography was avoided in the purifications of the steroidal spiroepoxides. This is an example of preparing enantiopure epoxyketones via aqueous Darzens reaction using chiral α-haloketone substrates.

One approach to cyclic carbonates via a three-component cyclization of phenacyl bromide, CO2, and aldehyde

A three-component cyclization reaction was designed for synthesizing cyclic carbonates in a single operation from phenacyl bromide, CO2, and aldehyde in the presence of lithium diisopropylamide (LDA). These novel reactions were achieved under extremely mild conditions to generate the target products in moderate to good yields within 10 min.

Facile epoxidation of α,β-unsaturated ketones with trans -3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane as an efficient oxidant

Application of trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane as an efficient oxygen source has been explored in the epoxidation of trans-chalcones. The reactions proceed under mild conditions at room temperature in alkaline solution to afford the corresponding epoxides in excellent yields.

IBX-I2 redox couple for facile generation of IOH and I +: Expedient protocol for iodohydroxylation of olefins and iodination of aromatics

(Chemical Equation Presented) IBX is readily reduced to IBAin the presence of molecular iodine in DMSO to generate hypoiodous acid (IOH), which reacts with a variety of olefins as well as R, β-unsaturated ketones leading to their respective iodohydrins with anti stereochemistry. The same redox chemistry in acetonitrile containing TFA produces iodonium ions for facile iodination of a variety of aromatic compounds in respectable isolated yields.

Darzens reaction promoted by KF/alumina: A novel stereoselective method for rapid and efficient synthesis of trans-α,β-epoxy ketones

The Darzens condensation of α-chloroacetophenone with various aromatic aldehydes mediated by potassium fluoride on alumina at room temperature resulted in formation of good to excellent yields of trans-α,β-epoxy ketones in short time periods. Copyright Ta

A novel and efficient darzens reaction catalyzed by magnesium bromide

The Darzens reaction of phenacyl bromide with aromatic aldehydes catalyzed by MgBr2 in the presence of an excess amount of triethylamine afforded trans-α,β-epoxy ketones in good yields.

Layered double hydroxides-supported diisopropylamide: Synthesis, characterization and application in organic reactions

The layered double hydroxides-supported diisopropylamide (LDH-DA) catalyst is found to be an efficient and selective solid base for aldol, Knoevenagel, Henry, Michael, transesterification and epoxidation reactions under liquid phase conditions. LDH-DA is synthesized by the interaction of lithium diisopropylamide with LDH-NO3 (as-synthesized) and calcined LDH-NO3. The LDH-DA (Mg/Al, 3/1) and their precursors are well characterized by using various instrumental techniques such as FT-IR, TGA and DTA, powder XRD, solid state 27Al MAS NMR spectroscopy, SEM and XPS (ESCA).