Furanone Derivatives Research Articles

Radiotracer Studies on the Formation of 2,5-Dimethyl-4-hydroxy-3(2H)-furanone in Detached Ripening Strawberry Fruits

The transformation of 12 radioactively labeled compounds into 2,5-dimethyl-4-hydroxy-3(2H)-furanone (DMHF), glycosidically bound DMHF, and 2,5-dimethyl-4-methoxy-3(2H)-furanone (DMMF) was investigated in detached ripening strawberry fruits (Fragaria × ananassa) over a 3-day period. Radiochemical analysis of the different fruit parts revealed that major portions of the applied radioactivity (up to 66%) remained in the stems and calyx. Incorporation levels of [2-14C]dihydroxyacetone, d-[1-3H]glucose, d-[U-14C]-glucose, d-[U-14C]glucose 6-phosphate, d-[U-14C]fructose, and d-[U-14C]fructose 1,6-bisphosphate into the total amount of furanone derivatives were 0.022, 0.032, 0.035, 0.147, 0.202, and 0.289% of the radioactivity entering the fruits, respectively. Minor amounts of radioactivity (<0.001%) were detected in the furanone structures after the administration of [1-14C]acetate and [3-14C]pyruvate. l-[1-14C]Fucose, l-[6-3H]fucose, l-[1-3H]rhamnose, l-[U-14C]threonine, l-[U-14C]lactaldehyde, and [2-14C]malonic acid were not transformed into DMHF or a derivative thereof. Keywords: Biosynthesis; carbohydrate metabolism; 2,5-dimethyl-4-hydroxy-3(2H)-furanone; Fragaria × ananassa; Rosaceae

Stability of naturally occurring 2,5-dimethyl-4-hydroxy-3 [2H]-furanone derivatives

The stability, in aqueous buffer solutions at different pH values (pH 2.0–8.0, interval: 1.5 pH units), of 2,5-dimethyl-4-hydroxy-3[2H]-furanone (Furaneol, DMHF, 1), its methoxy derivative 2,5-dimethyl-4methoxy-3[2H]-furanone (methoxyfuraneol, mesifurane, DMMF, 2 and the glycosidically bound forms DMHF β-D-glucopyranoside 3 and DMHF 6′-O-malonyl-β-Dglucopyranoside 4 was investigated over a period of 32 days at 23 °C. Only slight decomposition of 2 and 3 was observed, whereas 1 and 4 were found to be unstable at all pH values. In addition, 3 and 4 were subjected to enzymatic hydrolysis. In contrast to the rapid hydrolysis of 3, the malonylated glycoside, 4, remained unaffected by enzymatic treatment with β-glucosidase (Emulsin). Using a pectinolytic enzyme preparation (Rohapect D5L; Rohm, Darmstadt, Germany) with esterase activities, hydrolysis of 4 was achieved.

Chiroptical properties, structure, and absolute configuration of heterosubstituted 2(5H)-furanones

Chiroptical properties of a series of 3 and/or 4-heterosubstituted 2(5H)-furanones were investigated with respect to correlation with absolute configuration. The n - pi* and pi - pi* Cotton effects have been assigned on the basis of comparison with the UV spectra in solvents of varying polarity. It is demonstrated that the n - pi* transition in 4-amino substituted 2(5H)-furanones appears at shorter wavelength with respect to the a - pi* transition. With the exception of 4-pyrrolidino and 4-benzylamino substituted 2(5H)-furanones, other heterosubstituted 2(5H)-furanones follow the butenolide configurational rule (Gawronski et al. J. Org. Chem. 61:1513-1515, 1996). Absolute configuration of 2(5H)-furanone derivatives can also be assigned according to the sign of the Cotton effect (of unknown origin) at 200-230 nm. The structure of four representative sulfur and nitrogen substituted 2(5H)-furanones has been analyzed by X-ray diffraction. The results indicate planarity of the furanone ring and extended conjugation in 4-amino substituted 2(5H)-furanones. (C) 1997 Wiley-Liss, Inc.

Aldonolactones as chiral templates in the synthesis of thiolactones, 1,3-polyols and hydroxy amino acids

Abstract

Synthesis and reactions of 2‐[α‐(3,4‐disubstituted phenacyl)‐p‐substituted styryl]‐4H‐3,1‐benzoxazin‐4‐ones

AbstractConversion of β‐aroyl propionic acids into furanone derivatives (2) and benzoxazinone derivatives (3) for the study of the reactivity of these nucleus towards different nucleophilic and electrophilic reagents.

Tertiary alcohol synthesis from secondary alcohols via C–H insertion

Secondary alcohols are converted into 3(2H)-furanone derivatives via C–H insertion reaction, from which tertiary alcohols are prepared with retention of stereochemistry.

The synthesis of 11-oxabicyclo[6.2.1]undecenone derivatives

11-Oxabicyclo[6.2.1]undecenone derivatives 16 and 17 were synthesized via cycloalkylation of appropriately substituted monocyclic 3(2H)-furanone derivatives.

Asymmetric synthesis of butenolide and butyrolactone derivatives

2-Trimethylsiloxyfuran and 4-methoxy-2-trimethylsiloxyfuran, which are readily prepared from butenolide and methyl tetronate respectively, have been reacted with a series of homochiral ortho-esters and oxazolidine derivatives in the presence of Lewis acids to afford homochiral 2(5 H)-furanone derivatives. The structures of these products have been determined using nmr spectroscopy and, where possible, by X-ray analysis. Preliminary experiments have been carried out involving conjugate addition to these unsaturated lactones, demonstrating their potential as substrates for natural product synthesis.

STUDIES ON α-[6-(2′-METHOXYNAPHTHALENYL)-4-PHENYLPYRIMIDINYLTHIO]-β/-(4-PHENYLBENZOYL)PROPIONIC ACID AND THE BIOLOGICAL ACTIVITY OF SOME PRODUCTS

Abstract β-(4-phenylbenzoyl)acrylic acid I reacted with 6-(2′-methoxynaphthalenyl)-4-phenylpyrimidine-2(1H)thione to furnish α-[6-(2′-methoxynaphthalenyl)-4-phenylpyrimidinylthio]-β-(4-phenylbenzoyl)propionic acid II. Dehydration of acid II aforded furanone derivative III. The behaviour of III towards hydrazine hydrate, hydroxylamine hydrochloride, primary amines, aromatic hydrocarbons (under Friedel-Crafts conditions) and carbon nucleophiles (under Grignard conditions) has been investigated.

Reactions of β-dicarbonyl compounds with acyl cyanides catalyzed or promoted by metal centres in the homogeneous phase

The C–C bond-forming reaction between β-dicarbonyl compounds and acyl cyanides is catalyzed by nickel acetylacetonate or promoted by tin tetrachloride. Thus, β-diketones react with acyl cyanides in the presence of catalytic amounts of [Ni(acac)2] to give β-enamino diketones 3. β-Enamino keto esters 8 or β-enamino diesters 9 are obtained in the reactions of methyl acetoacetate or methyl malonate with acyl cyanides in the presence of stoichiometric amounts of SnCl4. The reactions of acyl cyanides with methyl malonate also afford furanone derivatives 10, whose structure has been determined, in one case, by a single-crystal X-ray analysis. β-Keto amides react with acyl cyanides to give pyrrolidine derivatives 13 both under catalytic conditions and stoichiometric conditions where an equimolar equivalent of promoter was used.

Macrolactonization-transannular aldol condensation approach to the taxane AB ring system

3-(3-butenyl)-5-[2-(1,3-dioxan-2-yl)ethyl]-2,4,4-trimethyl-2-cyclohexenone (13), containing the fully elaborated taxane A ring, was prepared from 4,4-dimethyl-2-cyclohexenone (43% for for four steps); two copper-catalyzed Grignard conjugate addition reactions on 4,4-dimethyl-2,5-cyclohexadienone (8) and 3-(3-butenyl)-2,4,4-trimethyl-2,5-cyclohexadienone (11) were employed as key transformations. Elaboration of (13) to the chloro keto acid 3-[3-(4-chloro-3-oxobutyl)-2,4,4-trimethyl-5-oxo-1(6)-cyclohexenyl]propanoic acid (6), was achieved via an epoxidation/regioselective chloride-mediated epoxide ring opening/Jones oxidation protocol (42% for three steps). Macrolactonization (59%) followed by chemoselective transannular aldol condensation within the resulting 11-membered bicyclic keto lactone 12,14,14-trimethyl-5-oxobicyclo[8.3.1]tetradeca-12-ene-3,6,11-trione (4), under thermodynamic control (51%), resulted in closure of the taxane B ring to afford the target 5-oxa-11,14,14-trimethyltricyclo[8.3.1.0 3 ,7]tetradeca-3(7),10-diene-4,12-dione (3) (2(5H)-furanone derivative)

Convenient Methods for the Preparation of Sulfur Substituted Allenecarboxylates

2-Sulfinyl- and 2-sulfonylallenecarboxylates, as new 1,1-diacceptor substituted allenes, were prepared starting from methyl 4-hydroxy-4-methyl-2-pentynoate by a [2,3]-sigmatropic rearrangement. The sulfoxides could be reduced to the corresponding allenyl sulfides. A 2(5H)-furanone derivative was prepared by a side-reaction.

A further selective pathway in thermal conversion of 2,5-epidioxy-2-alkoxy-2,5-dihydrofurans (2-alkoxyfuran endo-peroxides). Synthesis of the first 5-hydroperoxyfuran-2(5H)-ones

Thermal conversion of the epidioxydihydrofurans 1 leads, via dioxetanes 3, to the stereoisomeric dimers 4 which have a structural relationship with antitumour cyclic peroxides and represent convenient starting materials for several multifunctional compounds; their mild acid hydrolysis provides a convenient entry to the synthesis of the furanone derivatives 7 and 8 which are structurally related to biologically active products.

Bleaching Herbicide Flurtamone Interferes with Phytoene Desaturase

The mode of action of the furanone herbicide flurtamone and derivatives was investigated with cress seedlings and with the unicellular cyanobacterium Anacystis. Either in the light or in the dark these compounds inhibited the formation of alpha- and beta-carotene and all of the xanthophylls in the seedlings. Instead, phytoene, a precursor of colored carotenoids, was accumulated. In illuminated seedlings photooxidative destruction of chlorophyll was observed. The I(50) value of flurtamone inhibition of carotenoid biosynthesis in intact Anacystis cells and the K(1) value for interaction of flurtamone with phytoene desaturase with Anacystis thylakoids were 30 and 18 nanomoles, respectively. Concentrations of flurtamone which strongly inhibited carotenoid synthesis had no direct peroxidative activities and did not inhibit photosynthetic electron transport.

ChemInform Abstract: An Efficient Synthesis of 2(5H)‐Furanone and Furan Derivatives Using 3‐(Phenylthio)propenal as a 1,3‐Dipolar Synthon.

AbstractThe phenylthiopropenal (IV), prepared from acrolein (I) via 3‐(phenylthio)propionaldehyde (III), is converted into the 5‐substituted 3‐phenylthiofuranones (VII) by coupling with the organolithium compounds (V), lithiation with sBuLi and subsequent carboxylation.

Crystal structures of some 3-(hydroxymethylene)dihydro-2(3H)-furanone derivatives

The crystal structures of (Z)-3-(p-toluenesulfonyloxymethylene)dihydro-2(3H)-furanone (I), (E)-3-(methanesulfonyloxymethylene)dihydro-2(3H)-furanone (II), and (E)-3-(benzoyloxymethylene)dihydro-2(3H)-furanone (III) were solved by direct methods. The intensities of the diffractions were recorded using MoKα graphite monochromatized radiation, λ = 0.07107 nm. The compound I is monoclinic, space group P21/n, with a = 0.8615(2), b = 0.5955(2), c = 2.3883(5) nm, β = 93.27(2)°, V = 1.223(1) nm3, Z = 4, F(000) = 560, Dm = 1.43, Dx = 1.46 Mg m-3, μ = 0.27 mm-1. The structure was refined to R = 0.042 for 1 341 independent diffractions. Compound II is triclinic, space group P1, with a = 0.5840(2), b = 0.8232(2), c = 0.9827(3) nm, α = 97.68(3), β = 110.82(3), γ = 108.62(3)°, V = 0.402(1) nm3, Z = 2, F(000) = 200, Dm = 1.55, Dx = 1.59 Mg m-3, μ = 0.38 mm-1. The structure was refined to R = 0.041 for 952 independent diffractions. Compound III is monoclinic, space group P2/m with a = 0.9665(3), b = 1.1861(3), c = 0.9906(3) nm, β = 112.85(3)°, V = 1.046(2) nm3, Z = 4, F(000) = 456, Dm = 1.35, Dx = 1.38 Mg m-3, μ = 0.11 mm-1. The structure was refined to R = 0.048 for 1 115 independent diffractions. The configurations of the compounds I, II, and III are in agreement with the assignments made on the basis of the NMR spectra.

An efficient synthesis of 2(5H)-furanone and furan derivatives using 3-(phenylthio)propenal as a 1,3-dipolar synthon.

Various 2(5H)-furanone and furan derivatives were synthesized from 3-(phenylthio)propenal by a one-pot process via carbonyl addition of a range of organometallic reagents and subsequent sulfide-directed α-lithiatin followed by electrophilic trapping. This methodology was successfuly applied to the syntheses of quercus lactone and 2, 5-diarylfuran natural products.

ChemInform Abstract: Efficient and Flexible Syntheses of Paraconic Esters and Other Highly Substituted Furanone Derivatives from Methyl 2‐Siloxycyclopropanecarboxylates.

AbstractDeprotonation of the cyclopropanecarboxylate (I) with LDA and subsequent quenching of the intermediate enolate with the ketones (II) produces the adducts (III).

ChemInform Abstract: A Novel and Efficient Synthesis of 2(5H)‐Furanone Derivatives.

AbstractCross‐aldol reaction of the α‐keto dimethyl acetals (I) with the silyl enol ethers (II) or the ketones (IV) gives the adducts (III).

ChemInform Abstract: Synthesis of a 3(2H)‐Furanone Derivatives (IV) from Propargylic Alcohol (I), CO (II), and Phenyl Halide (III) Catalyzed by Transition Metal Complexes.

ChemInform Abstract: Synthesis of a 3(2H)‐Furanone Derivatives (IV) from Propargylic Alcohol (I), CO (II), and Phenyl Halide (III) Catalyzed by Transition Metal Complexes.