37174-94-0

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 536-74-3 phenylacetylene 
• 94-02-0 ethyl 3-oxo-3-phenylpropionate 
• 5720-05-8 4-methylphenylboronic acid 
• 870673-67-9 ethyl 2-diazo-3-oxo-5-phenylpent-4-ynoate 
• 14610-18-5 2-phenylethynyl boronic acid dimethyl ester 
• 3278-34-0 ethyl 2-(ethoxythiocarbonylthio)acetate 
• 3377-92-2 vinyl pivalate 
• 5324-64-1 2-(benzenesulfonyl)ethynylbenzene 
• 932-87-6 1-Bromo-2-phenylacetylene 
• 1247-08-1 Triphenyl-phenylethynyl-stannane 
• 623-48-3 ethyl iodoacetae 

Downstream Products

• 1259284-19-9 C₁₈H₁₉NO₅ 
• 858232-61-8 C₂₀H₁₉NO₃ 
• 91962-64-0 (S)-ethyl 4-phenylbuta-2,3-dienoate 

Relevant academic research and scientific papers

A straightforward and mild synthesis of functionalized 3-alkynoates

Diazoacetates in coupling reactions: CuI serves as an effective catalyst for coupling terminal alkynes with diazo compounds to generate 3-alkynoates (see scheme). This method is efficient (1:1 ratio of reactants), mild (room temperature), and simple (no a

Enantioselective Phosphine-Catalyzed Trimerization of γ-Aryl-3-butynoates via Isomerization/[3 + 2] Cyclization/Michael Addition Cascade

We disclose an l-isoleucine-derived amide phosphine-catalyzed trimerization of γ-aryl-3-butynoates, which undergo an isomerization to allenoate, [3 + 2] cyclization, and Michael addition cascade. Exocyclopentene derivatives bearing an all-carbon quaternar

Highly Enantioselective [3 + 2] Annulation of 3-Butynoates with β-Trifluoromethyl Enones Promoted by an Amine-Phosphine Binary Catalytic System

We report a highly enantioselective [3 + 2] annulation between 3-butynoates and β-trifluoromethyl enones, furnishing trifluoromethylated cyclopentenes with three contiguous stereogenic centers in good yields, high diastereoselectivities, and excellent enantioselectivities. A unique catalytic system consisting of a simple amine and a chiral phosphine was devised, and the synergistic play of Lewis basic amine and phosphine was crucial for alkyne isomerization and subsequent cyclization. The protocol disclosed herein allows facile activation of 3-butynoates in phosphine-mediated asymmetric transformations.

General [4 + 1] Cyclization Approach to Access 2,2-Disubstituted Tetrahydrofurans Enabled by Electrophilic Bifunctional Peroxides

A general [4 + 1] cyclization reaction of carbonyl nucleophiles with 2-iodomethylallyl peroxides, which function as unique electrophilic oxygen synthons, for the synthesis of a broad range of 2,2-disubstituted tetrahydrofurans is achieved under operationally simple conditions. The unprecedented asymmetric version of such reaction is also realized via chiral auxiliary-assisted cyclization, thus providing a distinct approach to access chiral tetrahydrofurans with high diastereoselectivities. The new method can be applied to the synthesis of core structure of posaconazole drug.

Copper-catalyzed 1,1-Arylalkylation of terminal alkynes with diazo esters and organoboronic acids

A novel copper-catalyzed 1,1-Arylalkylation of terminal alkynes with diazo esters and organoboronic acids is described. With this methodology, (E)-β-Aryl-β,γ-unsaturated esters can be easily constructed in good to excellent yields directly from readily available and inexpensive traditional coupling reagents.

Transformation of Carbonyl Compounds into Homologous Alkynes under Neutral Conditions: Fragmentation of Tetrazoles Derived from Cyanophosphates

Cyanophosphates (CPs) can be easily prepared from either ketones or aldehydes, and their reaction with NaN3-Et3N·HCl results in the formation of azidotetrazoles. Under microwave irradiation, successive fragmentation of the azidotetrazoles generates alkylidene carbenes that undergo [1,2]-rearrangement and are transformed into homologous alkynes. Treatment of ketone-derived CPs with TMSN3 and Bu2SnO as catalyst in toluene at reflux directly yields the corresponding internal alkynes, whereas the reaction of aldehyde-derived CPs with NaN3-Et3N·HCl in THF at reflux or TMSN3-Bu2SnO (cat.) in toluene at reflux provides homologous terminal alkynes in good yields. These reactions take place under neutral conditions and can be successfully extended to obtain alkynes that are not usually accessible from the corresponding carbonyl compounds by the Ohira-Bestmann or Shioiri procedures, which require basic conditions.

Bifunctional hydrogen-bond donors that bear a quinazoline or benzothiadiazine skeleton for asymmetric organocatalysis

Hydrogen-bond (HB)-donor catalysts that bear a 2-aminoquinazolin-4-(1H)-one or a 3-aminobenzothiadiazine-1,1-dioxide skeleton have been developed, and it has been shown that these catalyst motifs act similarly to other HB-donor catalysts such as thioureas. The highly enantioselective hydrazination of 1,3-dicarbonyl compounds was realized even at room temperature with up to 96 % ee for 2-aminoquinazolin-4-(1H)-one-type catalysts, which were more effective than the corresponding urea and thiourea catalysts. In addition, benzothiadiazine-1,1-dioxide-type catalysts were shown to promote the isomerization of alkynoates to allenoates with high enantioselectivity. To overcome the problem that the products were obtained as mixtures with the starting alkynoates, we developed the tandem isomerization and cycloaddition of alkynoates for the synthesis of advanced chiral compounds such as bicyclo[2.2.1]heptenes and 3-alkylidene pyrrolidine without a significant loss of enantioselectivity.

Wolff rearrangement of β-alkynyl-α-diazo-β-ketoesters: Light-induced acetylene-allene isomerization and its use for activation of enediynes

Irradiation of β-phenylethynyl-α-diazo-β-ketoester with 300 or 350nm light results in efficient and regioselective Wolff rearrangement producing only the product of alkynyl group migration. Addition of alcohols to the resulting α-oxoketene yields α-phenylethynyl-β-diester, which undergoes rapid (τ1min) tautomerization to 1,1-dicarbalkoxyallene. The latter then adds second molecule of alcohol in Michael fashion to form the final product, 2-(1-alkoxy-2-phenylvinyl)malonic ester. α-Phenylethynyl- β-ketoacid produced from the ketene in aqueous solutions does not isomerize to an allene but rather undergoes decarboxylation to give β,γ- acetylenic ester. Introduction of o-(3-hydroxy-1-propynyl) fragment in the structure of the parent α-diazo-β-ketoester allowed us to achieve two goals simultaneously: ring closure by intramolecular nucleophilic attack of propargyl alcohol on photo-generated ketene and the subsequent acetylene-allene rearrangement. The resulting enyne-allene undergoes spontaneous Myers-Saito cycloaromatization generating 1,4-biradical. In alcohol solutions, however, ketene reaction with solvent outcompetes the intramolecular process.

Reactions of CF3-substituted boranes with α-diazocarbonyl compounds

Boranes substituted with a CF3-group can be generated from methyl boronic esters RB(OMe)2 and Me3SiCF3/KF followed by treatment with Me3SiCl. These boranes are stable only in coordinating solvents, and due to the increased Lewis acidity of boron, react rapidly with α-diazocarbonyl compounds to give the products of transfer of the organic group from boron. Alkyl, aryl, vinyl, and alkynyl boronic esters can be used in this reaction.

Free-radical carboalkynylation and carboalkenylation of olefins

Free-radical three-component carboalkynylation and -alkenylation of olefins have been developed. These involve the addition, across the double bond of an unactivated olefin, of a radical species α- to an electron-withdrawing group and an alkenyl or alkynyl moiety, derived from the corresponding sulfones.