2009-96-3

Upstream product

• 6797-44-0 2-oximino-1-penyl-1,3-butanedione 
• 93-91-4 1-phenylbutan-1,3-dione 
• 2683-06-9 3,5-dioxo-5-phenylpentanal 
• 7664-93-9 sulfuric acid 
• 64-17-5 ethanol 
• 98-59-9 p-toluenesulfonyl chloride 
• 1205534-16-2 2-azido-1,3-dimethylimidazolinium chloride 
• 98-86-2 acetophenone 
• 2397-79-7 2-phenyl-4H-pyran-4-one 

Downstream Products

• 3282-32-4 2-diazo-acetophenone 
• 10488-87-6 ethyl 2-benzoylpropionate 
• 25745-47-5 5-benzoyl-4-methyl-1⁽²⁾H-pyrazole-3-carboxylic acid 
• 25745-41-9 5-benzoyl-4-methyl-1⁽²⁾H-pyrazole-3-carboxylic acid ethyl ester 
• 13298-79-8 1-phenyl-butane-1,2,3-trione-2-(triphenylphosphoranylidene-hydrazone) 
• 26037-05-8 1-(3-benzoyl-4-methyl-1H-pyrazol-5-yl)ethanone 
• 15021-43-9 dimethylsulfonium 1-benzoyl-2-oxopropylide 
• 4435-51-2 1-phenyl-butane-1,2,3-trione 
• 120242-37-7 2,2-dihydroxy-1-phenylbutane-1,3-dione 
• 32742-19-1 methyl 2-benzoylpropionate 
• 614-27-7 methyl 3-oxo-3-phenylpropionate 
• 16648-44-5 methyl α-acetylphenylacetate 
• 112370-88-4 2-Methoxy-3-oxo-3-phenylpropionsaeuremethylester 
• 52955-65-4 (5-methyl-2-phenyloxazol-4-yl)(phenyl)methanone 

Relevant academic research and scientific papers

Solvent-Directed Transition Metal-Free C-C Bond Cleavage by Azido-1,3,5-triazines and Their Stability-Reactivity Paradox

We report a solvent-directed and regioselective carbon-carbon bond cleavage of aryl ketones by azido-1,3,5-triazines (ATs), which is typically completed within 10 min in DMSO at room temperature, without using transition metal catalysts. The cleavage is driven by the steric hindrance in the adducts of aryl ketones and ATs, which is substantiated by DFT calculation. Our recent results showed that ATs present high reactivity in solution and high stability in solid state. This "stability-reactivity paradox"has been explained in light of the molecular and crystal structures of ATs.

Amino-modified Merrifield resins as recyclable catalysts for the safe and sustainable preparation of functionalized α-diazo carbonyl compounds

Amino-functionalized polystyrene polymers derived from Merrifield resins were prepared and characterized. These basic materials were successfully employed as heterogeneous catalysts in the diazo transfer reaction to 1,3-dicarbonyl compounds, furnishing the corresponding diazo compounds in good to excellent yields and in relatively short reaction times. In addition, the work-up and purification protocols are simple and do not generate large amounts of waste, which are important features in sustainable catalysis and environmentally benign processes. The feasibility of the recovery and reuse of the amino-modified catalysts was also verified, since they can be employed up to five times without appreciable loss of catalytic activity. This straightforward procedure can be readily scaled up to gram scale, enabling the wide application of this method. The synthetic potential was demonstrated through the two-step preparation of 2-amino-N-dodecylacetamide (ANDA), a small molecule of commercial relevance.

Photoinduced Diverse Reactivity of Diazo Compounds with Nitrosoarenes

A diverse reactivity of diazo compounds with nitrosoarene in an oxygen-transfer process and a formal [2 + 2] cycloaddition is reported. Nitosoarene has been exploited as a mild oxygen source to oxidize an in situ generated carbene intermediate under visible-light irradiation. UV-light-mediated in situ generated ketenes react with nitosoarenes to deliver oxazetidine derivatives. These operationally simple processes exemplify a transition-metal-free and catalyst-free protocol to give structurally diverse α-ketoesters or oxazetidines.

Taking diazo transfer to water: α-diazo carbonyl compounds from in situ generated mesyl azide

Mesyl azide generated in situ in aqueous medium converted a range of active methylene substrates into the corresponding diazo compounds in good yields and high purity with no need for chromatographic purification. The products thus obtained are suitable for the subsequent RhII-catalyzed O–H insertions with no need for chromatography in the interim.

A 'sulfonyl-azide-free' (SAFE) aqueous-phase diazo transfer reaction for parallel and diversity-oriented synthesis

Diazo transfer reactions are notoriously associated with the use of potentially explosive sulfonyl azides. The first 'sulfonyl-azide-free' (SAFE) protocol for producing diazo compounds from their active-methylene precursors via the Regitz diazo transfer reaction was developed and has displayed a remarkable substrate scope. It can be applied to generating arrays of diazo compounds for further evolution via combinatorial chemistry and a range of scaffold-generating transformations.

Cycloaddition of α-Diazocarbonyl Compounds and N-Tosylaziridines: Synthesis of Polysubstituted 2 H-1,4-Oxazines through Synergetic Catalysis of AgOTf/Cu(OAc)2

An impressive and new [3 + 3]-cycloaddition of α-diazocarbonyl compounds with N-tosylaziridines via synergetic catalysis of AgOTf and Cu(OAc)2 has been well described, which offers efficient access to highly substituted 2H-1,4-oxazine derivatives. A variety of α-diazocarbonyl compounds and N-tosylaziridines were compatible substrates with convenient operations under mild reaction conditions.

Rhodium(i)-catalyzed vinylation/[2 + 1] carbocyclization of 1,6-enynes with α-diazocarbonyl compounds

A sequential Rh(i)-catalyzed vinylation/[2 + 1]carbocyclization between enynes and diazo compounds has been developed. This transformation features a wide range of enynes and acceptor/acceptor diazo compounds, providing easy access to versatile vinyl-substituted azabicyclo[3.1.0]hexanes having a broad tolerance to functional groups.

Intrinsically Safe and Shelf-Stable Diazo-Transfer Reagent for Fast Synthesis of Diazo Compounds

We report a crystalline compound 2-azido-4,6-dimethoxy-1,3,5-triazine (ADT) as an intrinsically safe, highly efficient, and shelf-stable diazo-transfer reagent. Because the decomposition of ADT is an endothermal process (ΔH = 30.3 kJ mol-1), ADT is intrinsically nonexplosive, as proved by thermal, friction, and impact tests. The diazo-transfer reaction based on ADT gives diazo compounds in excellent yields within several minutes at room temperature. ADT is very stable upon >1 year storage under air at room temperature.

Rhodium(ii)-catalysed generation of cycloprop-1-en-1-yl ketones and their rearrangement to 5-aryl-2-siloxyfurans

Donor-acceptor cyclopropenes formed from enoldiazoketones undergo catalytic rearrangement to 5-aryl-2-siloxyfurans via a novel mechanism that involves a nucleophilic addition of the carbonyl oxygen to the rhodium-activated cyclopropene.

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular SN2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.