74812-79-6

Upstream product

• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 100-19-6 (4-nitrophenyl)ethanone 
• 115262-00-5 [chloro(difluoro)methyl]trimethylsilane 
• 555-16-8 4-nitrobenzaldehdye 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 1206-46-8 trimethyl(pentafluorophenyl)silane 
• 75-77-4 chloro-trimethyl-silane 

Downstream Products

• 7714-12-7 2-methoxy 4'-nitroacetophenone 
• 15982-64-6 1,4-bis(4-methoxyphenyl)butane-1,4-dione 
• 108791-69-1 1-(4-Methoxy-phenyl)-4-(4-nitro-phenyl)-butane-1,4-dione 
• 108791-66-8 1,4‐bis(4‐nitrophenyl)butane‐1,4‐dione 
• 120312-62-1 C₁₄H₁₁INO₃⁽¹⁺⁾*BF₄^(1-) 
• 120312-67-6 1-(4-nitrophenyl)-4-phenylbutane-1,4-dione 
• 1066-40-6 Trimethylsilanol 
• 130190-71-5 1-(4-Nitro-phenyl)-ethenol 
• 46417-99-6 2-nitro-1-(4-nitrophenyl)-1-ethanone 
• 62-23-7 4-nitro-benzoic acid 
• 517-25-9 trinitromethane 
• 1846-30-6 ω-(p-Toluolsulfonylamino)-4-nitro-acetophenon 
• 183435-02-1 3-Ethoxy-1-(4-nitro-phenyl)-5-phenylselanyl-pent-4-yn-1-one 
• 69746-39-0 5-(4-nitrophenyl)-2,3-dihydro-2,3-furandione 

Relevant academic research and scientific papers

Versatile and base-free copper-catalyzed α-arylations of aromatic ketones using diaryliodonium salts

A ligand and base-free copper catalyzed synthetic method for the efficient α-arylation of aromatic ketones is described. In order to avoid strong bases, ketone-derived silyl enol ethers were employed. Their reaction with diaryliodonium salts as aryl source provided the intermolecular C–C coupling displaying good functional group tolerance and requiring low catalyst loading.

σ-Bond initiated generation of aryl radicals from aryl diazonium salts

σ-Bond nucleophiles and molecular oxygen transform aryl diazonium salts into aryl radicals. Experimental and computational studies show that Hantzsch esters transfer hydride to aryl diazonium species, and that oxygen initiates radical fragmentation of the diazene intermediate to produce aryl radicals. The operational simplicity of this addition-fragmentation process for the generation of aryl radicals, by a polar-radical crossover mechanism, has been illustrated in a variety of bond-forming reactions.

C?O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non-Rubottom Oxidation

Malonyl peroxides act both as oxidants and reagents for C?O coupling in reactions with methyl and silyl enol ethers. In the proposed conditions, the oxidative C?O coupling of malonyl peroxides with enol ethers selectively proceeds, bypassing the traditional Rubottom hydroxylation of enol ethers by peroxides. It was observed that the oxidative [5+2] cycloaddition of malonyl peroxides and enol ethers is the key stage of the discovered process. Oxidative C?O coupling of silyl enol ethers leads to the formation of α-acyloxyketones with a free carboxylic acid group. A specially developed preparative one-pot procedure transforms ketones via silyl enol ethers formation and the following coupling into α-acyloxyketones with yields 35–88%. The acid-catalyzed coupling with methyl enol ethers gives remarkable products while retaining the easily oxidizable enol fragment. Furthermore, these molecules contain a free carboxylic acid group, thus these nontrivial products contain two usually incompatible acid and enol ether groups. (Figure presented.).

Enantioselective Mukaiyama–Michael Reaction Catalyzed by a Chiral Rhodium Complex Based on Pinene-Modified Pyridine Ligands

The rhodium complex Λ-Rh1 containing chiral pinene-modified pyridine ligands is prepared through a two-step synthetic procedure; it exhibits excellent reactivity and enantiocontrol towards the enantioselective Mukaiyama–Michael reaction of α,β-unsaturated 2-acyl imidazoles with silyl enol ethers, affording enantioenriched 1,5-dicarbonyl compounds in good yields (up to 99 %) with excellent enantioselectivities (up to 99 % ee).

Ring-Opening Diarylation of Siloxydifluorocyclopropanes by Ag(I) Catalysis: Stereoselective Construction of 2-Fluoroallylic Scaffold

A silver-catalyzed, defluorination ring-opening diarylation of siloxy 2,2-difluorocyclopropanes, with two arenes, to directly prepare polysubstituted 2-fluoroallylic compounds, is described. This multicomponent reaction proceeds smoothly in good stereoselectivity, which is due to a chelation-controlled addition of arenes to α-fluorinated ketone intermediate.

Synthesis of β-Amino Ketones by Addition of Aryl Methyl Ketones to Sulfinimines: Application to the Total Synthesis of HPA-12, Norsedamine, and Sedamine

Synthesis of β-sulfinamido ketones was accomplished by the addition of silyl enol ethers derived from arylmethyl ketones to chiral sulfinimines in excellent yield and selectivity. Application of the formed β-amino substituted ketones is exemplified in the total synthesis of sphingolipid HPA-12 and the sedamine alkaloids.

Difluorohomologation of ketones

A method for the homologation of ketones with the CF2 fragment is described. The reaction involves silylation, room-temperature difluorocyclopropanation of silyl enol ethers, and selective ring opening of cyclopropanes under acidic conditions. The whole three-step sequence is conveniently performed in a one-pot mode.

Halogenative difluorohomologation of ketones

A method for the difluorohomologation of ketones accompanied by halogenation of a C-H bond is described. The reaction involves silylation, difluorocarbene addition using Me3SiCF2Br activated by a bromide ion, and halogenation of intermediate cyclopropanes with N-bromo- or N-iodosuccinimide. The whole process is performed without isolation of intermediates. The resulting α,α-difluoro-β-halo-substituted ketones can be readily converted into fluorine containing pyrazole derivatives and oxetanes.

Lewis acid catalyzed enlargement of cyclic β-alkoxyenals and one-pot synthesis of polyfunctional enoxysilanes derived from aucubin with trimethylsilyldiazomethane

Pyrane to oxepane in one step: Highly regio- and stereoselective homologations dependent on the nature of carbonyl function and catalysts have been observed during the formation of enoxysilanes (see scheme). Trimethylsilyl trifluoromethanesulfonate (TMSOT

ScIII-Doped zeolites as new heterogeneous catalysts: mukaiyama aldol reaction

ScIII-doped solids based on zeolite materials have been investigated for the first time as catalysts in organic synthesis. Sc III-USY zeolite proved to be a novel and very efficient heterogeneous catalyst for the Mukaiyama aldol reaction. This easy-to-prepare catalyst exhibited wide scope and compatibility with functional groups and is very simple to use, easy to remove (by simple filtration), and is recyclable (up to three times without loss of activity).