- Thermal oxidation of 9′-cis-neoxanthin in a model system containing peroxyacetic acid leads to the potent odorant β-damascenone
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The potent odorant β-damascenone was formed directly from 9′-cis-neoxanthin in a model system by peroxyacetic acid oxidation and two-phase thermal degradation without the involvement of enzymatic activity. β-Damascenone formation was heavily dependent on pH (optimum at 5.0) and temperature, occurring over the two sequential phases. The first was incubation with peroxyacetic acid at 60°C for 90 min, and the second was at above 90°C for 20 min. Only traces of β-damascenone were formed on application of only one of the two phases. Formate and citrate solutions produced a much better environment for β-damascenone formation than acetate and phosphate. About 7 μg/L β-damascenone was formed from 5.8 mg/L 9′-cis-neoxanthin under optimal experimental condition. The detailed pathway by which β-damascenone is formed remains to be elucidated.
- Bezman, Yair,Bilkis, Itzhak,Winterhalter, Peter,Fleischmann, Peter,Rouseff, Russell L.,Baldermann, Susanne,Naim, Michael
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Read Online
- Cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp3)–H bonds
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A protocol for the cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp3)–H bonds with carboxylic acids was developed in this work. Mechanistic studies revealed that C(sp3)–H bond activation in the hydrocarbon was the turnover-limiting step and the in-situ formed [Co(III)]Ot-Bu did not engage in hydrogen atom abstraction (HAA) of a C–H bond. This protocol was successfully incorporated into a synthetic pathway to β-damascenone that avoided the use of NBS.
- Ren, Tian-Lu,Xu, Bao-Hua,Mahmood, Sajid,Sun, Ming-Xue,Zhang, Suo-Jiang
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supporting information
p. 2943 - 2948
(2017/04/26)
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- Rationalizing the formation of damascenone: Synthesis and hydrolysis of damascenone precursors and their analogues, in both aglycone and glycoconjugate forms
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Storage of megastigma-4,6,7-trien-3,9-diol (5), and megastigma-3,4-dien-7- yn-9-ol (6) in aqueous ethanol solution at pH 3.0 and 3.2 gave exclusively damascenone (1) and damascenone adducts at room temperature. The diol (5) had half-lives for the conversion of 32 and 48 h at pH 3.0 and pH 3.2, respectively. The acetylenic alcohol (6) had half-lives of 40 and 65 h at the same pH levels. In order to study the reactivity of the C-9 hydroxyl function in 5 and in the previously investigated allenic triol 2, two model compounds, megastigma-4,6,7-trien-9-ol (7) and megastigma-6,7-dien-9-ol (8) were synthesized. No 1,3-transposition of oxygen to form analogues of damascenone was observed when 7 and 8 were subjected to mild acidic conditions. Such transposition takes place only with highly conjugated acetylenic precursors such as 6 or tertiary allenic alcohols such as 2. The placement of glucose at C-3 of 5 and at C-9 of 6 gave the glycosides 9 and 10, respectively. The effect of such glucoconjugation was to increase the observed half-lives by a factor of only 1.6-1.7 for the allenic glucoside 9, and by 2.1-2.2 for the acetylenic glucoside 10. These studies indicate that the effect of glycosylation on damascenone formation is probably not important on the time scale of wine making and maturation.
- Daniel, Merran A.,Puglisi, Carolyn J.,Capone, Dimitra L.,Elsey, Gordon M.,Sefton, Mark A.
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scheme or table
p. 9183 - 9189
(2010/04/23)
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- New straightforward synthesis of β-damascenone and β-damascone derivatives from β-ionone via retro-α-ionol
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β-Damascenone and β-damascone derivatives, important fragrant compounds, were directly obtained from β-ionone by a new way via retro-α-ionol. Copyright Taylor & Francis Group, LLC.
- Campagnole,Delmond, Bernard
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p. 1077 - 1090
(2008/02/01)
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- New preparation methods for α-damascone, γ-damascone, and β-damascenone using pyronenes
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γ- and δ-Pyronenes are terpenic synthons easily available from myrcene. They are used as intermediates in the synthesis of α-damascone, γ-damascones, and β-damascenone. Copyright Taylor & Francis Group, LLC.
- Boulin, Bertrand,Taran, Martine,Miguel, Bernadette Arreguy-San,Delmond, Bernard
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p. 2579 - 2591
(2008/02/10)
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- Identification of (3S, 9R)- and (3S, 9S)-megastigma-6,7-dien-3,5,9-triol 9-O-β-D-glucopyranosides as damascenone progenitors in the flowers of Rosa damascena Mill.
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The progenitors of damascenone (1), the most intensive C 13-norisoprenoid volatile aroma constituent of rose essential oil, were surveyed in the flowers of Rosa damascena Mill. Besides 9-O-β-D-glucopyranosyl-3-hydroxy-7,8-didehydro-β-ionol (4b), a stable progenitor already isolated from the residual water after steam distillation of flowers of R. damascena Mill., two labile progenitors were identified to be (3S, 9R)- and (3S, 9S)-megastigma-6,7-dien-3,5,9-triol 9-O-β-D-glucopyranosides (2b) based on their synthesis and HPLC-MS analytical data. Compound 2b gave damascenone (1), 3-hydroxy-β-damascone (3) and 4b upon heating under acidic conditions.
- Suzuki, Masayuki,Matsumoto, Shigetaka,Mizoguchi, Masaya,Hirata, Satoshi,Takagi, Kazuteru,Hashimoto, Ikue,Yamano, Yumiko,Ito, Masayoshi,Fleischmann, Peter,Winterhalter, Peter,Morita, Tetuichiro,Watanabe, Naoharu
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p. 2692 - 2697
(2007/10/03)
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- Identification of a precursor to naturally occurring β-damascenone
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9-Hydroxymegastigma-3,5-dien-7-yne 8a was synthesised and shown to be identical to an intermediate found in the acid-catalysed conversion of 3,5,9-trihydroxymegastigma-6,7-diene 4 to β-damascenone 1, 3-hydroxydamascone 5 and megastigma-5-en-7-yne-3,9-diol 6. When subjected to acid hydrolysis, 8a produced β-damascenone 1, in high yield. Importantly, the hydrolysate was completely free of 3-hydroxydamascone 5.
- Puglisi, Carolyn J,Elsey, Gordon M,Prager, Rolf H,Skouroumounis, George K,Sefton, Mark A
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p. 6937 - 6939
(2007/10/03)
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- Acid-catalyzed hydrolysis of alcohols and their β-D-glucopyranosides
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The hydrolysis, in model wine at pH 3, of the allylic, homoallylic, and propargylic glycosides, geranylβ-D-glucopyranoside, [3'-(1'-cyclohexenyl)- 1'-methyl-2'-propynyl]-β-D-glucopyranoside, (3'RS,9'SR)(3'-hydroxy-5'- megastigmen-7-yn-9-yl)-β-D-glucopyranoside, (3',5',5'-trimethyl-3'- cyclohexenyl)-β-D-glucopyranoside, E-(7'-oxo-5',8'-megastigmadien-3'-yl)-β- D-glucopyranoside (3-hydroxy-β-damascone-β-D-glucopyranoside), and their corresponding aglycons has been studied. In general, aglycons were more rapidly converted to transformation products than were the corresponding glucosides. Glycoconjugation of geraniol in grapes is a process that reduces the flavor impact of this compound in wine, not only because geraniol is an important flavor component of some wines but also because the rate of formation of other flavor compounds from geraniol during bottle-aging is reduced. However, when flavor compounds such as β-damascenone are formed in competition with flavorless byproducts, such as 3-hydroxy-β-damascone, by acid-catalyzed hydrolytic reactions of polyols, then glycoconjugation is a process that could enhance as well as suppress the formation of flavor, depending on the position of glycosylation. (3'RS,9'SR)-(3'-Hydroxy-5'- megastigmen-7'-yn-9'-yl)-β-D-glucopyranoside hydrolyzed more slowly but gave a higher proportion of β-damascenone in the products than did the aglycon at 50 °C. Reaction temperature also effected the relative proportion of the hydrolysis products. Accelerated studies do not parallel natural processes precisely but only approximate them.
- Skouroumounis, George K.,Sefton, Mark A.
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p. 2033 - 2039
(2007/10/03)
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- C13-norisoprenoid glucoconjugates from lulo (Solanum quitoense L.) leaves
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With the aid of multilayer coil countercurrent chromatography, subsequent acetylation, and liquid chromatographic purification of a glycosidic mixture obtained from lulo (Solanum quitoense L.) leaves, three C13-norisoprenoid glucoconjugates were isolated in pure form. Their structures were elucidated by NMR, MS, and CD analyses to be the novel (6R,9R)-13-hydroxy-3-oxo-α-ionol 9-O-β-D-glucopyranoside (4a), the uncommon (3S,5R,8R)-3,5-dihydroxy-6,7-megastigmadien-9-one 5-O-β-D-glucopyranoside (citroside A) (5a), and the known (6S,9R)-vomifoliol 9-O-β-D-glucopyranoside (6a). Enzymatic treatment of compound 5a showed the formation of 3-hydroxy- 7,8-didehydro-β-ionone (7), an important lulo peeling volatile, which in its turn after chemical reduction and heated acid catalyzed rearrangement generates β-damascenone (9) and 3-hydroxy-β-damascone (10).
- Osorio, Coralia,Duque, Carmenza,Fujimoto, Yoshinori
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p. 1641 - 1645
(2007/10/03)
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- The chemistry of thujone. XVI. Versatile and efficient routes to safronitrile, β-cyclogeranonitrile, β-cyclocitral, damascones, and their analogues
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Thujone, a waste by-product of the Canadian forest industry, has been utilized as a starting material to develop a versatile synthetic route to the damascones (rose oil ketones) and related analogues.The synthetic sequence provides a route to β-cyclocitral (45), the latter having been previously converted to β-damascone (2).In addition, thujone-drived intermediates are converted to β-damascenone (48) and to intermediates that can be utilized for the preparation of damascone analogues.In conjunction with the above, an efficient route to safronitrile (42), β-cyclogeranonitrile (43), and β-cyclocitral (45) from 2,6-dimethylcyclohexanone has been developed.In summary, these studies afford an attractive versatile route to these important perfumery materials.
- Kutney, James P.,Gunning, Philip J.,Clewley, Robin G.,Somerville, John,Rettig, Steven J.
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p. 2094 - 2114
(2007/10/02)
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- Precursors of Damascenone in Fruit Juices
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The acid-catalysed reactions of 6,7-megastigmadiene-3,5,9-triol and the β-D-glucosides of 5-megastigmen-7-yne-3,9-diol and 3-hydroxy-β-damascenone have been studied in relation to the formation of damascenone.The results show that hydrolysis of the allene triol could account for damascenone formation in the juices of grapes and other fruits.
- Skouroumounis, George K.,Massy-Westropp, Ralph A.,Sefton, Mark A.,Williams, Patrick J.
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p. 3533 - 3536
(2007/10/02)
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- ISOLATION OF A GLUCOSIDIC PRECURSOR OF DAMASCENONE FROM LYCIUM HALIMIFOLIUM MIL.
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A precursor of damascenone (1), 3-(2,4-dihydroxy-2,6,6-trimethylcyclohexylidene)-1-methylprop-2-enyl β-D-glucopyranoside (4), was isolated from the leaves of Lycium halimifolium Mil. (Solanaceae) and characterized as its pentaacetate 5.
- Naef, Regula,Velluz, Alain,Thommen, Walter
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p. 6521 - 6522
(2007/10/02)
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- Norisoprenoids in Vitis vinifera White Wine Grapes and the Identification of a Precursor of Damascenone in These Fruits
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Twenty-four norisoprenoids, which are either free volatile components of juices of Vitis vinifera cvv.Chardonnay, Semillon and Sauvignon Blanc, or are liberated by glycosidase enzyme, or acid hydrolysis of extracts of these juices, have been identified.Eleven of these norisoprenoids are reported as grape products for the first time.The hypothetical 7-oxomegastigmane precursors, grasshopper ketone (5) and megastigm-5-en-7-yne-3,9-diol (10), as well as the related allene, 9-hydroxymegastigma-4,6,7-trien-3-one (6), have been observed for the first time, cooccurring with damascenone (1), 3-hydroxy-β-damascone (2), 3-oxo-β-damascone (3) and 3-oxo-α-damascone (4).Hydrolytic studies have shown that megastigm-5-en-7-yne-3,9-diol (10) is a precursor of damascenone (1) and 3-hydroxy-β-damascone (2) during wine conservation.
- Sefton, Mark A.,Skouroumounis, George K.,Massy-Westropp, Ralph A.,Williams, Patrick J.
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p. 2071 - 2084
(2007/10/02)
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- 172. β-Cleavage of Bis(homoallylic) Potassium Alkoxides. Two-Step Preparation of Propenyl Ketones from Carboxylic Esters. Synthesis of ar-Turmerone, α-Damascone, β-Damascone, and β-Damascenone
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The transformation of 36 bis(homoallylic) alcohols VII to alkenones IX and X via β-cleavage of their potassium alkoxides VIIa in HMPA has been investigated (cf.Scheme 2).These studies have established an order of β-cleavage for 2-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1,1-dimethyl-2-propenyl, and benzyl groups in alkoxides 49a-56a and have allowed a comparison between the β-cleavage reaction and the oxy-Cope rearrangement in alkoxides 74a-83a.As illustrative synthetic applications, a two-step preparation of propenyl ketones 15-42 from carboxylic esters is described, together with syntheses of ar-turmerone (48), α-damascone ((E)-71), β-damascone ((E)-109), and β-damascenone ((E)-111).
- Snowden, Roger L.,Linder, Simon M.,Muller, Bernard L.,Schulte, Karl H.
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p. 1858 - 1878
(2007/10/02)
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- Synthesis of (E)-1-Propenyl Ketones from Carboxylic Esters and Carboxamides by Use of Mixed Organolithium-Magnesium Reagents
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The novel reagents formed by combination of allylmagnesium chloride and a strong non-nucleophilic lithium base (LiNR2) convert non- or slowly enolizable carboxylic esters or carboxamides into 2-propenyl ketones which are protected from further reaction by their in situ conversion into enolates.This modified Grignard reaction is applied to efficient syntheses of α-damascone, β-damascone, β-damascenone, and various other (E)-1-propenyl ketones.
- Fehr, Charles,Galindo, Jose
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p. 228 - 235
(2007/10/02)
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- Process for the preparation of damascenone
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A novel method of preparing 1-crotonoyl-2,6,6-trimethylcyclohexa-1,3-diene comprises treating an ester of the formula STR1 with a proton acid under essentially anhydrous conditions.
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- Alkenoyl-cyclohexadienes
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New cycloaliphatic unsaturated ketones and their use as perfuming and odour-modifying agents in the manufacture of perfumes and perfumed products, and as flavouring and taste-modifying agents in the preparation of foodstuffs in general and imitation flavours for foodstuffs, beverages, animal feeds, pharmaceutical preparations and tobacco products. Methods for the preparation of said cycloaliphatic unsaturated ketones.
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- Cycloaliphatic unsaturated ketones as odour- and taste-modifying agents
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Process for the preparation of unsaturated cycloaliphatic ketones useful as perfuming and odour-modifying agents in the manufacture of perfumes and perfumed products, and as flavouring and taste-modifying agents in the aromatization of foodstuffs in general and imitation flavours for foodstuffs, beverages, animal feeds, pharmaceutical preparations and tobacco products. Compositions of matter relating to some of said unsaturated cycloaliphatic ketones which are new, and perfume- and flavouring compositions containing same.
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- 148. The synthesis of damascenone and β-damascone and the possible mechanism of their formation from carotenoids
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A brief synthesis of damascenone (5) from the acetylenic diol 2 and also that of β-damascone (8) from β-ionol, resembling the biogenetic synthesis, are described. A possible mechanism for the formation of damascenone from neoxanthin is proposed.
- Isoe, Sachihiko,Katsumura, Shigeo,Sakan, Takeo
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p. 1514 - 1516
(2007/10/11)
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- 147. Model reactions for the biosynthesis of damascone-related compounds and their preparative application
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We report a new general synthesis of damasconcs. In the presence of acids, 7, 8-dehydro-β-ionole (10) or the related diols 11 are converted into a mixture of β-damascone (2) and the 7, 8-dehydrotheaspiranes (19). In the same way the 6-hydroxy-7, 8-dehydro-α-ionoles 12 are transformed into a mixture of β-damascenone (3) and the 8-oxatheaspiranes (20). The reaction provides access to damascone derivatives 4-7 which have been found in nature. These synthetic experiments lend support to our hypotheses concerning the biogenesis of damascones from suitable carotenoids or their metabolites.
- Ohloff, Guenther,Rautenstrauch, Valentin,Schulte-Elte, Karl H.
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p. 1503 - 1513
(2007/10/10)
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