94540-79-1

Upstream product

• 1743-36-8 1-phenylbut-3-yn-1-ol 
• 100-52-7 benzaldehyde 
• 53949-11-4 γ-phenyl-α-phenylmethylene-Δ^β,γ-butenolide 
• 1008788-92-8 (2-oxo-5-phenyltetrahydrofuran-3-yl)-phosphonic acid diethyl ester 
• 17572-78-0 1,4-diphenylbut-3-yn-1-ol 
• 69158-04-9 2-(Hydroxy-phenyl-methyl)-4-oxo-4-phenyl-butyric acid methyl ester 
• 55980-63-7 Methyl-4-hydroxy-4-phenyl-2-butenoat 
• 26613-71-8 4-phenyl-2-methylenebutyrolactone 
• 591-50-4 iodobenzene 

Relevant academic research and scientific papers

A novel one pot synthesis of γ-butyrolactones

α-Arylidene-γ-phenyl-Δβ,γ-butenolides were converted to the respective γ-butyrolactones in methyl alcohol with sodium borohydride in presence of triethylamine in a single pot.

α-Alkylidene-γ-butyrolactone Formation via Bi(OTf)3-Catalyzed, Dehydrative, Ring-Opening Cyclizations of Cyclopropyl Carbinols: Understanding Substituent Effects and Predicting E/Z Selectivity

A Bi(OTf)3-catalyzed ring-opening cyclization of (hetero)aryl cyclopropyl carbinols to form α-alkylidene-γ-butyrolactones (ABLs) is reported. This transformation represents different chemoselectivity from previous reports that demonstrated formation of (hetero)aryl-fused cyclohexa-1,3-dienes upon acid-promoted cyclopropyl carbinol ring opening. ABLs are obtained in up to 89% yield with a general preference for the E-isomers. Mechanistically, Bi(OTf)3 serves as a stable and easy to handle precursor to TfOH. TfOH then catalyzes the formation of cyclopropyl carbinyl cations, which undergo ring opening, intramolecular trapping by the neighboring ester group, subsequent hydrolysis, and loss of methanol resulting in the formation of the ABLs. The nature and relative positioning of the substituents on both the carbinol and the cyclopropane determine both chemo- and stereoselective outcomes. Carbinol substituents determine the extent of cyclopropyl carbinyl cation formation. The cyclopropane donor substituents determine the overall reaction chemoselectivity. Weakly stabilizing or electron-poor donor groups provide better yields of the ABL products. In contrast, copious amounts of competing products are observed with highly stabilizing cyclopropane donor substituents. Finally, a predictive model for E/Z selectivity was developed using DFT calculations.

Synthesis and QSAR study of novel α-methylene-γ-butyrolactone derivatives as antifungal agents

Thirty-six new α-benzylidene-γ-lactone compounds based α-methylene-γ-butyrolactone substructure were prepared and characterized by spectroscopic analysis. All compounds were evaluated for antifungal activities in vitro against six plant pathogenic fungi and the half maximal inhibitory concentration (IC50) against Botrytis cinerea and Colletotrichum lagenarium were investigated. Compounds 5c-3 and 5c-5 with the halogen atom exhibited excellent fungicidal activity against B. cinerea (IC50?=?22.91, 18.89?μM). The structure-activity relationships (SARs) analysis indicated that the derivatives with electron-withdrawing substituents at the meta- or para-positions improves the activity. Via the heuristic method, the generated quantitative structure-activity relationship (QSAR) model (R2?=?0.961) revealed a strong correlation of antifungal activity against B. cinerea with molecular structures of these compounds. Meanwhile, the cytotoxicity of 20 representative derivatives was tested in the human tumor cells line (HepG2) and the hepatic L02 cells line, the result indicated that the synthesized compounds showed significant inhibitory activity and limited selectivity. Compound 5c-5 has the highest fungicidal activity with IC50?=?18.89?μM (against B. cinerea.) but low cytotoxicity with IC50?=?35.4?μM (against HepG2 cell line) and IC50?=?68.8?μM (against Hepatic L02 cell line). These encouraging results can be providing an alternative, promising use of α-benzylidene-γ-lactone through the design and exploration of eco-friendly fungicides with low toxicity and high efficiency.

Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters to synthesize γ-ketone esters

This work concerns the Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters with TMEDA as an additive. The isomerization proceeded under mild conditions and afforded γ-keto esters in high yield (up to 96%) within 2 h. Both (Z)- and (E)-γ-hydroxy-α,β-alkenoic esters were tolerated under the reaction conditions. This transformation involves the in situ formation of a dienolate intermediate from the easily accessible γ-hydroxy-α,β-alkenoic ester. The in situ generated dienolate can react with benzaldehyde and undergo a practical, useful tandem allylic isomerization-Aldol reaction to afford more functionalized compounds.

CO2-activation for γ-butyrolactones and its application in the total synthesis of (±)-heteroplexisolide e

An efficient nickel(0)-catalyzed highly regio- and stereoselective hydrocarboxylation of homopropargylic alcohols with ZnEt2 in the presence of CO2 (1 atm, balloon) to synthesize α-alkylidene- γ-butyrolactones is described. The catal

Synthesis and cytotoxic activity of γ-aryl substituted α-alkylidene-γ-lactones and α-alkylidene-γ-lactams

A series of 5-aryl-3-alkylidenedihydrofuran-2(3H)-ones 6a-g″ and 11a,b as well as 5-aryl-3-methylidenepyrrolidin-2-ones 10a-c and 12 were synthesized starting from 4-aryl-2-diethoxyphosphoryl-4-oxobutanoates 3a-g. Reaction sequence includes reduction or reductive amination of the carbonyl group, lactonization or lactamization step and finally the Horner-Wadsworth-Emmons olefination of aldehydes using thus obtained 5-aryl-3-diethoxyphosphoryl-3,4-dihydrofuran-2(5H)-ones 5a-g″ or 5-aryl-3-diethoxyphosphorylpyrrolidin-2-ones 9a-c. Furanones 6 and 11, as well as pyrrolidinones 10 and 12, were evaluated in vitro against mouse leukemia cell line L-1210 and two human leukemia cell lines HL-60 and NALM-6. Several of the obtained furanones proved to be very potent against all three cell lines with IC50 values lower than 6 μM. Structure-activity relationships of these compounds, as well as 5-alkyl or 5-arylmethyl-3-methylidenedihydrofuran-2(3H)-ones 13a-e, previously obtained in our laboratory, are discussed.

Spiroaziridines from 4-substituted α-ylidene-γ-butyro lactones

4-Substituted α-ylidene-γ-butyrolactones produce N-ethoxycarbonyl-spiroaziridino γ-lactone diastereomers on treatment with NsONHCO2Et and CaO. A good stereofacial preference is observed when the ring substituent is a phenyl group. These product

Tungsten(II)-carbene complex functions as a dicationic synthon: Efficient constructions of furan and pyran frameworks from readily available α,δ- and α,ε-alkynols

Treatment of tungsten-η1-α,δ- and -η1-α,ε-alkynols 4-6 with RCHO/BF3 · Et2O (R = alkyl, aryl) in cold diethyl ether effected cycloalkenation reaction, yielding tungsten-η1-furylidene and -η1- pyrylidene salts in excellent yields (>95%). The structures of these oxacarbeniums were elucidated through X-ray diffraction studies of the representative compounds 7 and 8 in addition to standard NMR and IR spectral data. In contrast with conventional metal carbeniums, these tungsten oxacarbeniums reacted with two molecules of nucleophiles such as H20, NaBH3CN, and Grignard reagents, resulting in α,α-double addition reactions to afford furan and pyran derivatives in good yields. In the hydride case, unsymmetric α,α-double addition of η1-furylidenium salts was achieved via treatment with NaBH4/MeOH. Organocuprates also effected double alkylations of these salts but in a distinct 1,3-addition pathway. The reactions of these oxacarbeniums with CH2N2 were examined; the outcome depends on their vinyl substituents. When the substituent is an aliphatic group, the carbenium species undergo highly diastereoselective cyclopropanation with CH2N2. For an aryl substituent, the reaction with CH2N2 yielded a new tungsten oxacarbenium with a significantly altered structure; in this case 13C- and 2H-labeling experiments were performed to elucidate the reaction mechanism.