33553-90-1

Upstream product

• 100-52-7 benzaldehyde 
• 922-67-8 propynoic acid methyl ester 
• 4519-46-4 methyl 2-bromoacrylate 
• 598-30-1 sec.-butyllithium 
• 594-19-4 tert.-butyl lithium 
• 109-72-8 n-butyllithium 
• 67-56-1 methanol 
• 201230-82-2 carbon monoxide 
• 4187-87-5 1-Phenyl-2-propyn-1-ol 

Downstream Products

• 14274-07-8 methyl trans-β-benzoylacrylate 
• 41158-32-1 methyl 4-oxo-4-phenylbut-2-ynoate 
• 56015-01-1 methyl 4-hydroxy-4-phenyl-(E)-but-2-enoate 
• 709631-38-9 (Z)-4-Hydroxy-2-iodo-4-phenyl-but-2-enoic acid methyl ester 
• 19522-28-2 (Z)-4-oxo-4-phenyl-but-2-enoic acid methyl ester 
• 1124276-26-1 4-(dihexylamino)-5-phenylfuran-2(5H)-one 
• 1124276-22-7 4-(butylamino)-5-phenylfuran-2(5H)-one 
• 1124276-36-3 5-phenyl-4-(1-phenylethylamino)furan-2(5H)-one 
• 1124276-30-7 4-(dibenzylamino)-5-phenylfuran-2(5H)-one 
• 6620-27-5 4,5-diphenylfuran-2(5H)-one 
• 944413-77-8 C₁₉H₁₅NO₃ 
• 944413-76-7 C₁₉H₁₅NO₃ 

Relevant academic research and scientific papers

Synthesis of New γ-Lactams with gem-Difluorinated Side Chains

A short and efficient approach has been designed for the synthesis of new γ-lactams that feature gem-difluorinated side-chains in position 4. The key steps involve 1,4-addition of nitroalkane anions on electrophilic gem-difluoroalkenes, followed by a cascade nitro reduction-heterocyclization. This flexible strategy also allows easy introduction of substituents in positions 3 or 5.

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.

Reactions of alkyl 4-hydroxybut-2-ynoates with arenes under superelectrophilic activation with triflic acid or HUSY zeolite: Alternative propargylation or allenylation of arenes, and synthesis of furan-2-ones

Reactions of alkyl 4-aryl(or 4,4-diaryl)-4-hydroxybut-2-ynoates [Ar(H or Ar')(OH)C4–C3≡C2–CO2Alk] with arenes under the action of triflic acid TfOH or HUSY zeolite result in the formation of two main compounds, aryl substituted furan-2-ones or products of propargylation of electron rich arenes. Key reactive intermediates in these transformations are the corresponding O,O-diprotonated forms of starting butynoates, Ar(H or Ar')(+OH2)C4–C3≡C2– C(=O+H)(OAlk), dehydration of which gives rise to mesomeric propargyl-allenyl cations Ar(H or Ar')(OH)4C+–C3≡C2–C(=O+H)(OAlk) ? Ar(H or Ar')(OH)4C = C3 = 2C+–C(=O+H)(OAlk), having two electrophilic centers on the carbons C4 and C2 respectively. Reactions of these species with arenes at C4 lead to products of arene propargylation, alternatively, reactions at C2 result in allenylation of arenes, followed by further transformation into furan-2-ones. Using quantum chemical calculations by the DFT method, it has been shown that the reactivity of such propargyl-allenyl cations is mainly explained by orbital factors. Plausible reaction mechanism is discussed.

Highly enantioselective catalytic methyl propiolate addition to both aromatic and aliphatic aldehydes

The excellent catalytic effect on methyl propiolate addition to a wide range of aromatic and aliphatic aldehydes promoted by inexpensive and commercially available BINOL-based ligand is reported. The catalyst systems showed high yields and excellent enantioselectivities for aromatic aldehydes, and excellent yields and high enantioselectivities for aliphatic aldehydes.

: NBu4NPF6 promoted regioselective cascade synthesis of functionally embellished naphthofurans under acid, metal & solvent free conditions

nBu4NPF6 mediated highly regioselective synthesis of functionally embellished naphthofurans has been achieved from easily available naphthols and propargyl alcohols through a cascade benzylation, oxacyclisation (5-exo dig) and isomerization under solvent free conditions. The reaction works in a short time through dibenzyl ether formation followed by the decomposition to the carbocation to furnish the high yielding products with large substrate scope. The synthetic utility of the products is demonstrated through C(sp3)-H functionalization. In addition, we investigated selected naphthofurans for their anti-amyloidogenic properties. Preliminary studies suggest that these are excellent inhibitors for amyloid formation, a hallmark for several neurodegenerative diseases.

Synthesis of β-allylbutenolides via one-pot copper-catalyzed hydroallylation/cyclization of γ-hydroxybutynoate derivatives

One-pot copper-catalyzed hydroallylation/lactone cyclization of γ-hydroxybutynoate derivatives was developed to afford β-allylbutenolides.

Synthesis of fluorenone and anthraquinone derivatives from aryl- and aroyl-substituted propiolates

Fluorenone derivatives were generated from aryl-substituted propiolates via a cobalt-catalyzed Diels-Alder reaction/DDQ-oxidation and Friedel-Crafts-type cyclization. Several functional groups are tolerated, and good to excellent overall yields (up to 89%) could be achieved. For the synthesis of anthraquinone derivatives, aroyl-substituted propiolates were applied in a zinc iodide catalyzed Diels-Alder reaction with 1,3-dienes. The subsequent DDQ oxidation and Friedel-Crafts-type cyclization led to symmetrical as well as some unsymmetrical anthraquinones in good to excellent yields of up to 87% over the three-step reaction sequence.

Synthesis of 3,4-dihalogenated furan-2-(5H)-ones by electrophilic cyclization of 4-hydroxy-2-alkynoates

Functionalized 3,4-dihalogenated furan-2(5H)-ones can be readily prepared in moderate to good yields by treating 4-hydroxy-4-arylbut-2-ynoate derivatives with ICl, IBr, and I2. Both halogen atoms of the electrophile are incorporated in the product. The resulting halides can further afford polycyclic aromatic compounds using known palladium-catalyzed coupling reactions.

Robust eco-friendly protocol for the preparation of γ-hydroxy- α,β-acetylenic esters by sequential one-pot elimination-addition of 2-bromoacrylates to aldehydes promoted by LTMP in 2-MeTHF

An efficient and widely applicable preparation of γ-hydroxy-α, β-acetylenic esters is described by means of a one-pot dehydrobromination of a 2-bromoacrylate ester with LTMP followed by the electrophilic addition of the transient propiolate to different aldehydes in the eco-friendly solvent 2-MeTHF. The Royal Society of Chemistry 2012.