77550-11-9Relevant articles and documents
Oxidative cleavage of C-C double bond in cinnamic acids with hydrogen peroxide catalysed by vanadium(v) oxide
Horvat, Monika,Iskra, Jernej
, p. 2073 - 2081 (2022/04/07)
We have developed a cheap, green, mild and environmentally friendly method for the selective cleavage of carbon-carbon double bonds with a 30% aqueous solution of hydrogen peroxide as the oxidant and vanadium(v) oxide as the catalyst. The selectivity of the oxidative cleavage of cinnamic acid derivatives 1 depends on the substituents and the solvent used (DME - MeOCH2CH2OMe, TFE - 2,2,2-trifluoroethanol or MeCN). In DME, p-hydroxy derivatives were selectively converted to benzaldehyde derivatives 2, in TFE, oxidative cleavage led to the formation of benzoquinone derivatives 4, while in MeCN, cinnamic acid derivatives were selectively converted to benzoic acid derivatives 3. Ferulic acid 1a was quantitatively and selectively converted to vanillin 2a in a 91% isolated yield on a gram scale. Dimeric difurandione 1a′ was isolated as an intermediate, which was confirmed by in situ ATR-IR spectroscopy, while the formation of diols or epoxides was not observed. The analogous styrene derivative, 4-vinylguaiacol 1e was also selectively converted to either vanillin 2a or 2-methoxyquinone 4a in a high yield. The green metric for the conversion of ferulic acid to vanillin by different methods was calculated and compared to our method, and showed that our method has better environmental parameters.
Laccase-catalyzed oxidative phenolic coupling of vanillidene derivatives
Constantin, Mihaela-Anca,Conrad, Juergen,Beifuss, Uwe
supporting information, p. 2375 - 2379 (2013/02/21)
The laccase-catalyzed oxidative phenolic coupling of vanillidene derivatives using aerial oxygen as the oxidant has been developed. Depending on the substitution pattern of the vanillidene double bond of the substrate, either dilactones, dihydrobenzo[b]furans or biphenyls are formed.
Laccase-catalyzed dimerization of ferulic acid amplifies antioxidant activity
Adelakun, Oluyemisi E.,Kudanga, Tukayi,Parker, Ayesha,Green, Ivan R.,Le Roes-Hill, Marilize,Burton, Stephanie G.
experimental part, p. 29 - 35 (2012/05/19)
Enzymatic modification can be used to enhance the bioactive properties of phenolic compounds. The present study employed laccase from Trametes pubescens to catalyze the modification of ferulic acid in a monophasic or biphasic system, as a way of enhancing
Stereochemistry of phellinsin A: A concise synthesis of α-arylidene-γ-lactones
Kim, Eungsoo,Hyeong, Kyu Lee,Hwang, Eui-Il,Kim, Sung-Uk,Woo, Song Lee,Lee, Sangku,Jung, Sang-Hun
, p. 1231 - 1238 (2007/10/03)
Phellinsin A (1a) was prepared in a concise way, thereby elucidating the relative stereochemistry of the aryl and carboxylic acid groups in 1a. The synthesis employed selective monohydrolysis of the dilactones derived from oxidative dimerization of cinnamic acid derivatives. This approach provided a practical synthetic route to α-arylidene-γ-lactones. Copyright Taylor & Francis, Inc.
Regioselective dimerization of ferulic acid in a micellar solution
Larsen, Erik,Andreasen, Mette F.,Christensen, Lars P.
, p. 3471 - 3475 (2007/10/03)
Dehydrodimers of hydroxycinnamates play an important role in the cross-linking of plant cell walls. An aqueous solution of quaternary ammonium salts with a long aliphatic chain is known to spontaneously organize itself into micelles with the ionic part at the outer sphere. It is shown that regioisomeric ferulic acid dehydrodimers can be obtained in one step from trans-ferulic acid after attachment to these micelles and using the biomimetic peroxidase-H2O2 system. The surfactant hexadecyltrimethylammonium hydroxide yielded trans-4-(4-hydroxy-3-methoxybenzylidene)-2-(4-hydroxy-3-methoxyphenyl)-5- oxotetrahydrofuran-3-carboxylic acid (25%), (E, E)-4,4′-dihydroxy-5,5′-dimethoxy-3,3′-bicinnamic acid (21%), and trans-5-[(E)-2-carboxyvinyl]-2-(4-hydroxy-3-methoxyphenyl)7-methoxy-2,3- dihydrobenzofuran-3-carboxylic acid (14%), whereas the surfactant tetradecyltrimethyl-ammonium bromide gave 4-cis, 8-cis-bis(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclo[3.3.0]octane-2,6-dione (18%) as the main product. The use of micelles appears to be not only a new way to synthesize regioisomeric ferulic acid dehydrodimers but may also help to understand the regiospecificity of dimeric hydroxycinnamate formation in vivo.
Synthesis of 4,8-Bis(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclooctan-2-ones and Determination of their Relative Configuration via Long-range
Quideau, Stephane,Ralph, John
, p. 653 - 660 (2007/10/02)
A short synthesis of the furofuranoid lignan, 4-cis,8-cis-bis(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclooctan-2-one (MEL), was accomplished via a simple regioselective hydride reduction of the dilactone parent octane-2,6-dione>, followed by deoxygenation of the lactone-lactol intermediate via silane hydride transfer.The 4-trans-8-cis(iso-MEL) and the 4-cis-8-trans(epi-MEL) isomers, and a fourth related compound, featuring a 3-fused 5-membered ring skeleton were additionally formed.All four compounds were fully characterized by use of 1D and 2D NMR techniques.Examination of the long-range coupled proton network by delayed COSY experiments allowed determination of the relative configuration of these 4,8-diaryl-3,7-dioxabicyclooctan-2-one structures.The pathways followed by these long-range proton couplings and implications of the long-range and vicinal couplings with respect to favoured conformations are discussed.
Lignin-Feruloyl Ester Cross-links in Grasses. Part 2. Model Compound Syntheses
Ralph, John,Helm, Richard F.,Quideau, Stephane
, p. 2971 - 2980 (2007/10/02)
Five compounds which model the various structures produced when feruloyl esters are copolymerized into lignins have been synthesized.These models represent the lignin-feruloyl-polysaccharide structures which have been theorized to exist in the Graminaceae but have yet to be isolated.Complete spectroscopic characterization provides important chemical-shift information to facilitate the identification of these linkages in native lignins and synthetic DHP polymers.Methyl 5-O-feruloyl>-α-L-arabinofuranoside, a model for the α-linkage of feruloyl esters to lignin, was prepared as a mixture of threo and erythro isomers by addition of methyl 5-O-(E)-feruloyl-α-L-arabinofuranoside (FA-Ara) to the quinone methide derived from 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol (guaiacylglycerol-β-guaiacyl ether).Methyl 5-O-feruloyl>-α-L-arabinofuranoside, a β-aryl ether model, was prepared by a method analogous to one used for the synthesis of guaiacylglycerol-β-guaiacyl ether; FA-Ara was added to 4-acetoxy-β-bromo-3-methoxyacetophenone, and the product was hydroxymethylated and reduced.The peracetate of methyl 5-O--α-L-arabinofuranoside, a compound which models the attack of lignin radicals on the β-position of the feruloyl ester, was prepared by elimination of the β-proton from the quinone methide derived from ethyl 3-hydroxy-3-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propanoate.As in the preparation of synthetic copolymers between coniferyl alcohol andFA-Ara, only a single geometrical isomer was produced.Synthesis of both isomers of derived compounds and detailed NMR analysis indicated that this was the expected Z-isomer.A model for β-5 coupled products, 3-acrylic acid bis(methyl 5-deoxy-α-L-arabinofuranosid-5-yl) ester, was obtained as a cis/trans mixture in 55percent yield by radical coupling of FA-Ara using silver(I) oxide.Finally, the crossed β-β-compound 4,8-exo-bis(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclooctan-2-one (MEL) was obtained, in admixture with its isomer iso-MEL, pinoresinol, and the dilactone 4,8-exo-bis-(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclooctan-2,6-dione, from mixed radical coupling of coniferyl alcohol and ferulic acid via silver(I) oxide.
Synthesis and 1H N.M.R. Spectroscopic Analysis of Some 3,7-Dioxabicyclooctane Lignans
Velde, Vincent Vande,Lavie, David,Gottlieb, Hugo E.,Perold, Guido W.,Scheinmann, Feodor
, p. 1159 - 1164 (2007/10/02)
Within the framework of a synthetic project towards the preparation of the natural germination inhibitor 2,6-diaryl-3,7-dioxabicyclooctane, several molecules with the same bicyclic skeleton were prepared and their 1H n.m.r. spectra are described in detail.For the symmetrical systems particularly, the spectra exhibited second-order features and were interpreted analytically or, when necessary, by computer simulation.These n.m.r. data enabled a conformational analysis of the ring system.
Anodic Oxidation of 4-Hydroxycinnamic Acids and Related Phenols
Nishiyama, Atsuko,Eto, Hideo,Terada, Yukimasa,Iguchi, Masanobu,Yamamura, Shosuke
, p. 2845 - 2852 (2007/10/02)
Anodic oxidation of 4-hydroxycinnamic acids, 4-hydroxycinnamides and related phenols was carried out at a controlled potential, using an undivided cell, to afford the corresponding asatone-, isoasatone-, pinoresinol- or podophyllotoxin-type compounds.Furthermore, the corresponding dihydroxy compounds were also electrolyzed at a controlled potential to give different dienones depending on the side chains.Keywords - neolignan; electrochemical oxidation; Diels-Alder reaction; biomimetic synthesis
