501416-52-0

Upstream product

• 101-41-7 benzeneacetic acid methyl ester 
• 1455-13-6 deuteromethanol 
• 36140-84-8 1-(3,5-dimethyl-1H-pyrazol-1-yl)-2-phenylethan-1-one 
• 103-80-0 phenylacetyl chloride 
• 22979-35-7 Methyl phenyldiazoacetate 

Relevant academic research and scientific papers

Copper on charcoal: Cu0nanoparticle catalysed aerobic oxidation of α-diazo esters

By using a charcoal supported nano Cu0catalyst (Cu/C), a highly efficient oxidation of α-diazo esters to α-ketoesters with molecular oxygen as the sole oxidant has been developed. In the presence of the Cu/C catalyst, 2-aryl-α-diazo esters with both electron-donating and electron-withdrawing groups can be oxidized to the corresponding α-ketoesters efficiently. Furthermore, this Cu/C catalyst can catalyse the reaction of aryl α-diazo ester with water to form aryl ketoester, 2-aryl-2-hydroxyl acetate ester and 2-aryl acetate ester. In this case, water is split by α-diazo ester, and the diazo group is displaced by the oxygen or hydrogen atom in water. Mechanistic investigation showed that the reaction of α-diazo ester with oxygen proceeds through a radical pathway. In the presence of 2,2,6,6-tetramethyl piperidine nitrogen oxide, the reaction of α-diazo ester with oxygen is dramatically inhibited. Furthermore, the reaction of α-diazo ester with water is investigated by an isotopic tracer method, and GCMS detection showed that a disproportionation reaction occurred between α-diazo ester and water.

Nitrone/Imine Selectivity Switch in Base-Catalysed Reaction of Aryl Acetic Acid Esters with Nitrosoarenes: Joint Experimental and Computational Study

Herein we report a mild and diastereoselective access to ketonitrones by reacting easily available aryl acetic acid esters and other active methylene compounds, with nitrosoarenes under catalytic loading of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) at room temperature. Depending on the substitution pattern and nature of the aryl moiety, a switch toward the formation of imines can be observed. The mechanistic framework is put to scrutiny by experimental and theoretical studies, pointing to the formation of a nitroso aldol intermediate, whose fate toward one of the competing pathways, namely hydride transfer or elimination, would depend upon the NOH/CHα relative acidities. (Figure presented.).

Triazabicyclodecene: An effective isotope exchange catalyst in CDCl 3

(Chemical Equation Presented) We describe the first effective H/D exchange reaction with acidic substrates in CDCl3 at room temperature. The particularly mild reaction conditions involved (solvent, base, and temperature) allow the chemoselective deuteration of ketones over esters. An NMR study was conducted with the aim of rationalizing the results obtained in the presence of TBD as catalyst.

Resolution of secondary alcohols using 2-acyl-3-phenyl-l-menthopyrazoles as enantioselective acylating agents

The chelation of AlCl3 with N-acylpyrazoles leads to structural fixation of the acyl moiety and an acceleration in the rate of acylation of secondary alcohols. The chiral environment of the fixed acyl moiety of 2-acyl-3-phenyl-l-menthopyrazole 2 causes diastereofacial selectivity in the reaction with secondary alcohols, and thus 2 behaves as an enantioselective acylating agent. By the use of 2.4 molar equivalents of racemic 1-phenylethanol 3a, 2-acetyl-3-phenyl-l-menthopyrazole 2a afforded (S)-1-phenylethyl acetate (S)-4aa enantioselectively and unreacted 3a was recovered with (R)-configuration. Furthermore, the inverse configurational preferences were observed to give (R)-4aa and (S)-3a by the addition of strongly basic amines, which sometimes behaved as catalysts for enolate formation from 2 and AlCl3. These dramatic changes in stereoselective preference should be useful properties of 2-acyl-3-phenyl-l-menthopyrazole 2 as an enantioselective acylating agent.

Gas-phase Rearrangements of Deprotonated Ketoximes, Ketoxime Ethers, and Aldoximes. A Negative-ion Beckmann Rearrangement

Evidence is presented which indicates that the pronounced loss of water from deprotonated ketoximes involves specific proton transfer followed by a negative-ion Beckmann rearrangenment.For example, Me2C=NO- -> -CH2(Me)C=NOH -OH> -> CH2=C=NCH2- + H2O.Deprotonated aldoximes, e.g.MeCH=NO-, fragment in this way, but also undergo the competing process MeCH=NO- -> MeC=NOH -> -OH> -> -CH2CN + H2O.Other rearrangements occur when proton transfer to oxygen does not occur; e.g.Ph2C=NO- PhC=NOPh -> PhO- + PhCN.