7515-15-3

Upstream product

• 67-56-1 methanol 
• 2216-24-2 3-(4-nitrophenyl)-2-propynoic acid 
• 51738-11-5 methyl (Z)-2-bromo-3-(4-nitrophenyl)-2-propenoate 
• 636-98-6 p-nitrobenzene iodide 
• 922-67-8 propynoic acid methyl ester 
• 7647-01-0 hydrogenchloride 
• 4891-38-7 phenylpropynoic acid methyl ester 
• 555-16-8 4-nitrobenzaldehdye 
• 937-31-5 (4-Nitrophenyl)acetylene 
• 201230-82-2 carbon monoxide 
• 623-47-2 propynoic acid ethyl ester 

Downstream Products

• 18352-52-8 (Z)-2-[Bis-(2-hydroxy-ethyl)-amino]-3-(4-nitro-phenyl)-acrylic acid methyl ester 
• 137201-68-4 E-methyl β-morpholino-p-nitrocinnamate 
• 137201-73-1 E-methyl β-(N,N-diethylamino)-p-nitrocinnamate 
• 137201-76-4 Z-methyl β-(N,N-diethylamino)-p-nitrocinnamate 
• 78089-38-0 (E)-methyl 3-(4-nitrophenyl)-3-phenylthiopropenoate 
• 78089-39-1 (Z)-methyl 3-(4-nitrophenyl)-3-phenylthiopropenoate 
• 10004-51-0 5-(4-nitro-phenyl)-isoxazol-3-one 
• 1598408-64-0 C₁₀H₁₀N₂O 
• 1598408-65-1 C₁₇H₁₆N₂O 
• 2216-24-2 3-(4-nitrophenyl)-2-propynoic acid 
• 1598408-82-2 C₁₀H₈N₂O₃ 
• 1598408-83-3 C₁₇H₁₄N₂O₃ 
• 1598408-44-6 1-(4-(2-(methylcarbamoyl)ethynyl)phenyl)-3-(4-chloro-3-(trifluoromethyl)phenyl)urea 
• 1598408-45-7 1-(4-(2-(1-phenylethylcarbamoyl)ethynyl)phenyl)-3-(4-chloro-3-(trifluoromethyl)phenyl)urea 

Relevant academic research and scientific papers

Z-Selective phosphine promoted 1,4-reduction of ynoates and propynoic amides in the presence of water

Phosphine-mediated reductions of substituted propynoic esters and amides in the presence of water yield the partially reduced α,β-unsaturated esters and amides with highZ-selectivity. The competitivein situ ZtoE-isomerization of the product in some cases lowers theZtoEratios of the isolated α,β-unsaturated carbonyl products. Reaction time and the amounts of phosphine and water in the reaction mixture are the key experimental factors which control the selectivity by preventing or reducing the rates ofZ- toE-product isomerization. Close reaction monitoring enables isolation of theZ-alkenes with high selectivities. The computational results suggest that the reactions could be highlyZ-selective owing to the stereoselective formation of theE-P-hydroxyphosphorane intermediate.

Acetylenic Replacement of Albicidin's Methacrylamide Residue Circumvents Detrimental E/Z Photoisomerization and Preserves Antibacterial Activity

The natural product albicidin is a highly potent inhibitor of bacterial DNA gyrase. Its outstanding activity, particularly against Gram-negative pathogens, qualifies it as a promising lead structure in the search for new antibacterial drugs. However, as we show here, the N-terminal cinnamoyl moiety of albicidin is susceptible to photochemical E/Z isomerization. Moreover, the newly formed Z isomer exhibits significantly reduced antibacterial activity, which hampers the development and biological evaluation of albicidin and potent derivatives thereof. Hence, we synthesized 13 different variants of albicidin in which the vulnerable para-coumaric acid moiety was replaced; this yielded photostable analogues. Biological activity assays revealed that diaryl alkyne analogues exhibited virtually undiminished antibacterial efficacy. This promising scaffold will therefore serve as a blueprint for the design of a potent albicidin-based drug.

trans-Selective hydrocyanation of ynoates, ynones and ynoic acids catalyzed by nucleophilic phosphines

trans-Selective hydrocyanation of ynoates and ynones in the presence of TMSCN and an alcohol additive are catalyzed by nucleophilic phosphines. The trisubstituted E-olefin products of anti-addition of hydrogen cyanide to the alkyne are produced with high regio- and stereoselectivity. The alcohol additive reacts with TMSCN to produce hydrogen cyanide in situ. Ynoic acids undergo the phosphine catalyzed hydrocyanation in the presence of TMSCN under aprotic conditions only. In these reactions, TMSCN reacts with the acid to generate hydrogen cyanide and the silyl ester which, unlike the acid, undergoes phosphine catalyzed hydrocyanation and gives the stereo-defined E-2-cyano-acrylic acids after work up.

Asymmetric Transfer Hydrogenation of gem-Difluorocyclopropenyl Esters: Access to Enantioenriched gem-Difluorocyclopropanes

Catalytic enantioselective access to disubstituted functionalized gem-difluorocyclopropanes, which are emerging fluorinated motifs of interest in medicinal chemistry, was achieved through asymmetric transfer hydrogenation of gem-difluorocyclopropenyl este

Heptalene Synthesis by Addition of Aryl Acetylenes to Azulenes

Abstract: Aryl acetylenes bearing electron-withdrawing groups have been found that canadd to azulenes and yield 1,2-substituted heptalenes. Theoretical studies of thereaction mechanism helped to design the candidate molecules that have then beentested in

Catalytic, transition-metal-free semireduction of propiolamide derivatives: Scope and mechanistic investigation

We report a transition-metal-free trans-selective semireduction of alkynes with pinacolborane and catalytic potassium tert-butoxide. A variety of 3-substituted primary and secondary propiolamides, including an analog of FK866, a potent nicotinamide mononucleotide adenyltransferase (NMNAT) inhibitor, are reduced to the corresponding (E)-3-substituted acrylamide derivatives in up to 99% yield with >99:1 E/Z selectivity. Mechanistic studies suggest that an activated Lewis acid-base complex transfers a hydride to the α-carbon followed by rapid protonation in a trans fashion.

Oxidant- and additive-free simple synthesis of 1,1,2-triiodostyrenes by one-pot decaroboxylative iodination of propiolic acids

A metal- and oxidant-free facile synthesis of a range of 1,1,2-triiodostryrene derivatives has been developed which utilizes a simple decarboxylative triiodination of propiolic acids using molecular iodine and sodium acetate in a one-pot manner. Electron-

Relative Rates of Metal-Free Azide-Alkyne Cycloadditions: Tunability over 3 Orders of Magnitude

The thermal (3 + 2) dipolar azide-alkyne cycloaddition, proceeding without copper or strained alkynes, is an underutilized ligation with potential applications in materials, bioorganic, and synthetic chemistry. Herein, we investigate the effects of alkyne substitution on the rate of this reaction, both experimentally and computationally. Electron-withdrawing groups accelerate the reaction, providing a range of relative rates from 1.0 to 2100 between the slowest and fastest alkynes studied. Unexpectedly, aryl groups conjugated to the alkyne significantly retard the reaction rate. In contrast, a sulfonyl, ester-substituted alkyne is reactive enough that it couples with an azide at room temperature in a few hours. This reactivity scale should provide a guide to those who wish to use this ligation under mild conditions.

Relative Rates of Metal-Free Azide-Alkyne Cycloadditions: Tunability over 3 Orders of Magnitude

The thermal (3 + 2) dipolar azide-alkyne cycloaddition, proceeding without copper or strained alkynes, is an underutilized ligation with potential applications in materials, bioorganic, and synthetic chemistry. Herein, we investigate the effects of alkyne substitution on the rate of this reaction, both experimentally and computationally. Electron-withdrawing groups accelerate the reaction, providing a range of relative rates from 1.0 to 2100 between the slowest and fastest alkynes studied. Unexpectedly, aryl groups conjugated to the alkyne significantly retard the reaction rate. In contrast, a sulfonyl, ester-substituted alkyne is reactive enough that it couples with an azide at room temperature in a few hours. This reactivity scale should provide a guide to those who wish to use this ligation under mild conditions.

Rhodium(III)-Catalyzed Redox-Neutral Cascade [3 + 2] Annulation of N-Phenoxyacetamides with Propiolates via C-H Functionalization/Isomerization/Lactonization

A Rh(III)-catalyzed cascade [3 + 2] annulation of N-phenoxyacetamides with propiolates under mild conditions using the internal oxidative O-N bond as the directing group has been achieved. This catalytic system provides a regio- and stereoselective access to benzofuran-2(3H)-ones bearing exocyclic enamino motifs with exclusive Z configuration selectivity, acceptable to good yields and good functional group compatibility. Mechanistic investigations by experimental and density functional theory studies suggest that a consecutive process of C-H functionalization/isomerization/lactonization is likely to be involved in the reaction.