75414-82-3

Upstream product

• 239094-37-2 ethyl-2-diazo-3-hydroxy-3-(4-nitrophenyl)-propanoate 
• 838-57-3 ethyl 4-nitrobenzoylacetate 

Downstream Products

• 1287721-35-0 methyl 2-{(2-ethoxy-1-(4-nitrobenzoyl)-2-oxoethyl)[(2,2,2-trichloroethoxy)carbonyl]amino}-3-(phenylthio)acrylate 
• 1364737-01-8 4-ethyl 3-methyl 2-(dimethylamino)-5-(4-nitrophenyl)furan-3,4-dicarboxylate 

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.

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.

Catalytic Enantioselective Cloke–Wilson Rearrangement

Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding dihydrofurans in the presence of a chiral phosphoric acid as the catalyst. The reaction involves activation of the donor-acceptor cyclopropane substrate by the

Amine-mediated synthesis of amides from 1,3-dicarbonyl compounds through a domino diazo transfer/aminolysis process

The dual role of amines as both catalysts and substrates for the synthesis of diazo compounds or carboxamides from 1,3-dicarbonyl compounds is described herein. In the presence of a suitable diazo transfer agent, primary and cyclic secondary amines act as basic catalysts for the diazo transfer reaction to malonates, β-keto esters, and β-diketones. Depending on the structure of the 1,3-dicarbonyl compound and the nucleophilicity of the amine, the resulting α-diazo-β-keto ester undergoes cleavage of the acyl group to give amides. A multifunctionalized γ-azido-α-diazo-β-keto ester was cleanly prepared in good yields by this one-pot protocol under practical and safe conditions, being employed in a Knoevenagel-type condensation with aromatic aldehydes to give densely functionalized diazo azido compounds. Further treatment of these unsaturated γ-azido-α-diazo-β-keto esters with primary amines readily furnished the corresponding α-azidocinnamamides in high yields, which were used in the synthesis of novel indole-2-carboxamides through the rhodium-catalyzed intramolecular C–H insertion.

Iron-Catalyzed Annulation of 1,2-Diamines and Diazodicarbonyls for Diverse and Polyfunctionalized Quinoxalines, Pyrazines, and Benzoquinoxalines in Water

A novel and facile iron-catalyzed tandem annulation of o-phenylenediamines and diazocarbonyls in water for the construction of polyfunctionalized quinoxalines has been developed. The key strategy includes the one-pot domino N?H insertion, cyclization, and

Regioselective Synthesis of Dihydrothiophenes and Thiophenes via the Rhodium-Catalyzed Transannulation of 1,2,3-Thiadiazoles with Alkenes

A method for the regioselective synthesis of a wide range of dihydrothiophenes was developed from the rhodium-catalyzed transannulation of 1,2,3-thiadiazoles with aliphatic, aromatic, and heteroaromatic alkenes. Tandem rhodium-catalyzed transannulation of 1,2,3-thiadiazoles with alkenes followed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation was also demonstrated for the one-pot regioselective synthesis of various thiophenes. Advantages of the present method include a broad substrate scope, wide functional group compatibility, and high regioselectivity.

Diazo transfer reaction to 1,3-dicarbonyl compounds with sulfonyl azides catalyzed by molecular sieves

A simple and effective heterogeneous catalyst based on zeolite-type materials has been developed for the diazo transfer reaction involving 1,3-dicarbonyl compounds and tosyl azide. α-Diazo carbonyl compounds were obtained under mild conditions in good to high yields using commercial molecular sieve 4A or analogues as the catalyst. The best catalyst was found to be 4A-1000, a synthetic potassium-free nepheline obtained by heating molecular sieve 4A at 1000 C. Characterization of the resulting aluminosilicate by XRD, FTIR and SEM-EDS analysis confirmed the change of the crystal structure. Besides being nontoxic and inexpensive, the heterogeneous catalyst was readily removed by filtration and could be reused at least for four runs without any special treatment.

Synthesis of 2-aminofurans and 2-unsubstituted furans via carbenoid-mediated [3 + 2] cycloaddition

An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.

A mild, efficient method for the oxidation of α-diazo-β-hydroxyesters to α-diazo-β-ketoesters

A wide variety of α-diazo-β-ketoesters can be prepared in good overall yields via a two-step sequence involving addition of ethyl lithiodiazoacetate to aliphatic, aromatic, and conjugated aldehydes followed by mild oxidation with the Dess-Martin periodina