A new route to 2-alkenyl-1,3-dicarbonyl compounds, intermediates in the synthesis of dihydrofurans

Antonioletti, Roberto; Bovicelli, Paolo; Malancona, Savina

doi:10.1016/s0040-4020(01)01173-5

Cited by 59 publications

(30 citation statements)

References 9 publications

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“…Encouraged by the simplicity and efficiency of our method in constructing the tricyclic skeleton possessing a fused and functionalized tetrahydrothiophene ring in a stereoselective manner, we felt that the enones 1a,b and acrylate 1d, [10] containing the key furyl moiety at the β-position, would be suitable for constructing other carbo-and heterocycles fused to oxanorbornenes. We chose allylmalonate 6a and its homoallyl analog 6b as the Michael donors for the synthesis of precursors suitable for the IMDAF reaction (Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…We note that in contrast to the predominance of exo-cis isomers 4 and 8 over exo-trans isomers 5 and 9 in the case of tetrahydrothiophenes 4,5 ( Table 1) and cyclopentanes 8,9 (Table 2), respectively, we obtained exo-trans isomers 13 as the major products in the case of pyrrolidines Table 3. Michael addition of diallylamine (10) [a] to β-furylacrylate 1d and furylidenemalonate 1e followed by an IMDAF reaction of Michael adducts 11. Table 3, and see also the discussion of the NMR and computational results below).…”

Section: Resultsmentioning

confidence: 99%

“…Michael acceptors 1a-e were prepared according to literature methods. [9][10][11] Computational Methodology: All calculations were performed at the RHF/3-21G* level of theory with the JAGUAR program. [12] Complete vibrational analyses were performed to characterize the transition state and ground state geometries.…”

Section: Methodsmentioning

confidence: 99%

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Synthetic and Theoretical Investigations on the Construction of Oxanorbornenes by a Michael Addition and Intramolecular Diels–Alder Furan Reaction

et al. 2008

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The conjugate addition of nucleophiles such as allylmercaptan, allyl‐ and homoallylmalonate and diallylamine to β‐furyl enones and acrylate, provides the Michael adducts in good yield. A facile intramolecular Diels–Alder reaction between the unsaturated tether and the furan diene ensues when these adducts are heated in a solvent such as toluene orxylene to afford the cycloadducts in good yield and excellent stereoselectivity in most cases. The structure and stereochemistry of these cycloadducts were confirmed by extensive NMR experiments and X‐ray crystallography. Quantum chemical calculations on the transition state and product geometries suggest that the formation of the cycloadducts, in which the newly formed ring is exo‐fused to the oxanorbornene framework, is favored over the endo‐fused product due to less strain in the former and its transition state.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthetic and Theoretical Investigations on the Construction of Oxanorbornenes by a Michael Addition and Intramolecular Diels–Alder Furan Reaction

et al. 2008

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“…Consequently, in the present work, we report the regio-and stereoselective synthesis of highly functionalized biologically relevant dihydrofurans bearing arylsulfonyl moiety 6. Previously reported synthesis of dihydrofuran derivatives include the reactions of sulfur ylide with α-ylidene-β-diketones via [4+1] annulation reaction, 18,19 one-step cyclization of β-ketosulfides of benzothiazole and aldehydes in ionic liquids, 20 reaction of β-ketopolyfluoroalkane sulfones with aldehydes, 21 reactions of 1,3-dicarbonyl compounds with appropriate olefins, [22][23][24] or α-bromonitroalkenes. 25 Cyclization as well as ring enlargement reaction are mostly used for the construction of dihydrofurans.…”

Section: Introductionmentioning

confidence: 99%

A facile regio- and stereoselective synthesis of trans-ethyl 5-aroyl-4-aryl-2-[(arylsulfonyl)methyl]-4,5-dihydrofuran-3-carboxylates

Harikrishnan¹,

Rajesh²,

Almansour³

et al. 2013

Arkivoc

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A library of novel trans-ethyl 5-aroyl-4-aryl-2-[(arylsulfonyl)methyl]-4,5-dihydrofuran-3-carboxylates were synthesized regio-and stereoselectively in good yields by a three-component domino reaction of ethyl-3-oxo-4-(arylsulfonyl)butanoates, aromatic aldehydes and Nphenacylpyridinium bromide in presence of triethylamine in acetonitrile under heating. This transformation generates C-O, C-C and C=C bonds and presumably proceeds via an α,β-unsaturated ketosulfonyl ester generation/Michael addition/intramolecular cyclisation domino sequence.

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“…Isobutyryl acetate esters are commercially attractive because of their applications as intermediates in the synthesis of heterocycles such as furan, pyrazolone, quinolone (Antonioletti et al, 2002;Jung et al, 2002;Shetty and Moffett, 2006;Wang and Hollingsworth, 1999). There is a dearth of information on the synthesis of isobutyryl acetate esters.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Modeling and Optimization of Immobilized Candida antarctica Lipase B Catalysed Synthesis of Butyl-4-Methyl-3-Oxopentanoate using Response Surface Methodology

Yadav¹,

Shinde²

2012

International Journal of Chemical Reactor Engineering

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Response surface methodology (RSM) was used to model and optimize the immobilized Candida antarctica lipase B catalysed synthesis of butyl-4-methyl-3-oxopentanoate. To determine optimum conditions of the transesterification, a four-factor and five-level central composite rotatable design (CCRD) was used. The factors studied were enzyme load (A), reaction temperature (B), methyl-4-methyl-3-oxopentanoate concentration (C) and n-butanol concentration (D). A quadratic polynomial regression model was used to analyze the experimental data at a 95% confidence level (p < 0.05). The results indicated that the RSM approach gave reasonable results for the optimization of the reaction parameters in the range of tested parameters. The optimal conditions for the enzymatic reaction were obtained at 0.01 mol of methyl-4-methyl-3-oxopentanoate and 0.03 mol of n-butanol using 104 mg of Novozym 435 at 55• C and 300 rpm for 6 h. Under these conditions, the transesterification percentage was 87 %. Further, kinetic modelling of the enzymatic synthesis was illustrated. Initial rate data and progress curve data were used to arrive at a suitable model. The kinetics was found to obey the ternary complex ordered bi-bi model with inhibition by the substrate methyl-4-methyl-3-oxopentanoate. The values of kinetic parameters obtained from nonlinear regression analysis were found to be Vmax of 0.04 mol/L.min; Km(A) 0.11 mol/L; Km(B) 2 mol/L and Ki(A) 2.2 mol/L.

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A new route to 2-alkenyl-1,3-dicarbonyl compounds, intermediates in the synthesis of dihydrofurans

Cited by 59 publications

References 9 publications

Synthetic and Theoretical Investigations on the Construction of Oxanorbornenes by a Michael Addition and Intramolecular Diels–Alder Furan Reaction

Synthetic and Theoretical Investigations on the Construction of Oxanorbornenes by a Michael Addition and Intramolecular Diels–Alder Furan Reaction

A facile regio- and stereoselective synthesis of trans-ethyl 5-aroyl-4-aryl-2-[(arylsulfonyl)methyl]-4,5-dihydrofuran-3-carboxylates

Kinetic Modeling and Optimization of Immobilized Candida antarctica Lipase B Catalysed Synthesis of Butyl-4-Methyl-3-Oxopentanoate using Response Surface Methodology

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