15626-54-7

Upstream product

• 1795-96-6 phenylalanine ethyl ester 
• 620-79-1 Ethyl 2-benzylacetoacetate 
• 56409-75-7 ethyl 2-benzyl-3-oxo-3-phenylpropanoate 
• 2021-28-5 ethyl dihydrocinnamate 
• 73901-01-6 p-nitrobenzenesulfonyl azide 
• 3081-24-1 H-Phe-OEt 
• 100-39-0 benzyl bromide 
• 1002717-68-1 benzyl-malonic acid ethyl ester methyl ester 
• 3182-93-2 ethyl 2-amino-3-phenylpropanoate hydrochloride 
• 98516-80-4 ethyl 2-formyl-3-phenylpropionate 
• 623-73-4 diazoacetic acid ethyl ester 

Downstream Products

• 1421-34-7 α-hydrazinobenzenepropanoic acid 
• 60030-15-1 2-Hydrazono-3-phenylpropionsaeureaethylester 
• 103-36-6 ethyl 3-phenyl-2-propenoate 
• 15399-27-6 ethyl 2-hydroxy-3-phenylpropanoate 
• 132629-24-4 ethyl 2-bromo-2-fluoro-3-phenylpropionate 
• 4610-69-9 (Z)-ethyl cinnamate 
• 4192-77-2 ethyl cinnamate 
• 37129-21-8 (E)-ethyl 3-phenyl-2-(2-phenylhydrazono)propanoate 
• 1007356-05-9 ethyl (E)-2-hydrazono-3-phenylpropionate 
• 1007356-15-1 ethyl (Z)-2-hydrazono-3-phenylpropionate 

Relevant academic research and scientific papers

Polymer-bound diazonium salts for the synthesis of diazoacetic esters

Starting from Merrifield resin, various polymer-bound diazonium salts were prepared. Upon treatment with amino acid esters, resulting the appropriate triazenes, the corresponding diazoacetic esters were formed by basic cleavage. Scope and limitation of th

Catalytic Asymmetric Homologation of Ketones with α-Alkyl α-Diazo Esters

The homologation of ketones with diazo compounds is a useful strategy to synthesize one-carbon chain-extended acyclic ketones or ring-expanded cyclic ketones. However, the asymmetric homologation of acyclic ketones with α-diazo esters remains a challenge due to the lower reactivity and complicated selectivity. Herein, we report the enantioselective catalytic homologation of acetophenone and related derivatives with α-alkyl α-diazo esters utilizing a chiral scandium(III) N,N′-dioxide as the Lewis acid catalyst. This reaction supplies a highly chemo-, regio-, and enantioselective pathway for the synthesis of optically active β-keto esters with an all-carbon quaternary center through highly selective alkyl-group migration of the ketones. Moreover, the ring expansion of cyclic ketones was accomplished under slightly modified conditions, affording a series of enantioenriched cyclic β-keto esters. Density functional theory calculations have been carried out to elucidate the reaction pathway and possible working models that can explain the observed regio- and enantioselectivity.

A sustainable catalytic enantioselective synthesis of norstatine derivatives

Norstatine derivatives are of important value in pharmaceutical science. However, their catalytic asymmetric synthesis is rare. We developed a sustainable method via chiral phosphoric acid (CPA)-[Rh(OAc)2]2 co-catalyzed multi-component reactions (MCR) of diazoacetates with alcohol/water and imines. This method allows us to synthesize a library of 45 norstatines with excellent enanotioselectivites and broad substrate scope which includes anti-α-aryl-norstatines 11-1, anti-α-alkyl-norstatines 11-2, syn-α-hydro-norstatines 11-3 and syn-α-aryl-norstatines 11-4. The sustainability of this method lies in the reliable scalability, improved safety, and reusable [Rh(OAc)2]2 catalyst. The synthetic value of norstatine derivatives was demonstrated by preparing oxazolinone 14, ezetimibe analogue 15, and Taxol C-13 chain 16. Mechanistic study reveals that the synergetic catalysis of CPA and [Rh(OAc)2]2 is essential to maintain chemo- and enantioselectivity. Control experiments support the mechanism where the reactions proceed through the trapping of hyper-reactive oxonium ylides with imines. Shortly, we report herein the sustainable catalytic enantioselective synthesis of both syn- and anti-norstatine derivatives. We believe that this method might shed light on the sustainable synthesis of norstatine derivative-based drug candidates.

Practical Application of the Aqueous 'Sulfonyl-Azide-Free' (SAFE) Diazo Transfer Protocol to Less α-C-H Acidic Ketones and Esters

The earlier described 'sulfonyl-Azide-free' ('SAFE') protocol for diazo transfer to CH-Acidic 1,3-dicarbonyl compounds (and their similarly activated congeners) has been extended to the less reactive monocarbonyl substrates, which previously required a se

Method for synthesizing alpha-diazoesters compound by using microwave at normal pressure

The invention discloses a method for synthesizing an alpha-diazoesters compound by using microwave at normal pressure. An esters compound and P-toluenesulfonyl azide are used as initial raw materials,1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) is used as a catalyst, the alpha-diazoesters compound can be generated in 30 minutes by virtue of a diazo transfer reaction under a microwave assisting heating condition, and the alpha-diazoesters compound can further generate a functional product. The organic reaction rate of the method is multiple times faster than the traditional heating method, the reaction efficiency is high, the operation is simple and convenient, the synthetic reaction condition is mild, the product type is rich, and the functional group is diversified.

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.

Catalytic Enantioselective Protonation/Nucleophilic Addition of Diazoesters with Chiral Oxazaborolidinium Ion Activated Carboxylic Acids

A new chiral Br?nsted acid derived from carboxylic acid and a chiral oxazaborolidinium ion (COBI), as an activator, is introduced. This acid was successfully applied as a catalyst for the highly enantioselective protonation/nucleophilic addition of diazoesters with carboxylic acids.

Copper-Mediated Deuterotrifluoromethylation of α?Diazo Esters

A copper-mediated deuterotrifluoromethylation of α?diazo esters under the promotion of deuterium oxide (D2O) has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethylation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. Moreover, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.

Trifluoromethylthiolation and Trifluoromethylselenolation of α-Diazo Esters Catalyzed by Copper

α-Diazo esters are smoothly converted into the corresponding trifluoromethyl thio- or selenoethers by reaction with Me4NSCF3or Me4NSeCF3, respectively, in the presence of catalytic amounts of copper thiocyanate. This straightforward method gives high yields under neutral conditions at room temperature and is applicable to a wide range of functionalized molecules, including diverse α-amino acid derivatives. It is well-suited for the late-stage introduction of trifluoromethylthio or -seleno groups into drug-like molecules.

gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors

A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.