23726-93-4Relevant articles and documents
Thermal oxidation of 9′-cis-neoxanthin in a model system containing peroxyacetic acid leads to the potent odorant β-damascenone
Bezman, Yair,Bilkis, Itzhak,Winterhalter, Peter,Fleischmann, Peter,Rouseff, Russell L.,Baldermann, Susanne,Naim, Michael
, p. 9199 - 9206 (2005)
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.
Cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp3)–H bonds
Ren, Tian-Lu,Xu, Bao-Hua,Mahmood, Sajid,Sun, Ming-Xue,Zhang, Suo-Jiang
supporting information, p. 2943 - 2948 (2017/04/26)
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.
Rationalizing the formation of damascenone: Synthesis and hydrolysis of damascenone precursors and their analogues, in both aglycone and glycoconjugate forms
Daniel, Merran A.,Puglisi, Carolyn J.,Capone, Dimitra L.,Elsey, Gordon M.,Sefton, Mark A.
scheme or table, p. 9183 - 9189 (2010/04/23)
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.
New straightforward synthesis of β-damascenone and β-damascone derivatives from β-ionone via retro-α-ionol
Campagnole,Delmond, Bernard
, p. 1077 - 1090 (2008/02/01)
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.
New preparation methods for α-damascone, γ-damascone, and β-damascenone using pyronenes
Boulin, Bertrand,Taran, Martine,Miguel, Bernadette Arreguy-San,Delmond, Bernard
, p. 2579 - 2591 (2008/02/10)
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.
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.
Suzuki, Masayuki,Matsumoto, Shigetaka,Mizoguchi, Masaya,Hirata, Satoshi,Takagi, Kazuteru,Hashimoto, Ikue,Yamano, Yumiko,Ito, Masayoshi,Fleischmann, Peter,Winterhalter, Peter,Morita, Tetuichiro,Watanabe, Naoharu
, p. 2692 - 2697 (2007/10/03)
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.
Identification of a precursor to naturally occurring β-damascenone
Puglisi, Carolyn J,Elsey, Gordon M,Prager, Rolf H,Skouroumounis, George K,Sefton, Mark A
, p. 6937 - 6939 (2007/10/03)
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.
Acid-catalyzed hydrolysis of alcohols and their β-D-glucopyranosides
Skouroumounis, George K.,Sefton, Mark A.
, p. 2033 - 2039 (2007/10/03)
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.
C13-norisoprenoid glucoconjugates from lulo (Solanum quitoense L.) leaves
Osorio, Coralia,Duque, Carmenza,Fujimoto, Yoshinori
, p. 1641 - 1645 (2007/10/03)
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).
Precursors of Damascenone in Fruit Juices
Skouroumounis, George K.,Massy-Westropp, Ralph A.,Sefton, Mark A.,Williams, Patrick J.
, p. 3533 - 3536 (2007/10/02)
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.
