- A convenient transformation of 2-alkylidenecycloalkanones into alkyl-substituted bicyclo[ n.1.0]alkan-1-ols: Application to the synthesis of capsaicin
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Treatment of 2-alkylidenecycloalkanones with hydrogen iodide in benzene and subsequent reaction of the obtained -iodo ketones with zinc dust in THF in the presence of chlorotrimethylsilane or titanium(IV) chlorotriisopropoxide led to exo- and endo-(n+3)-alkylbicyclo[n.1.0]alkan-1-ols in high yields. Cyclization of the intermediate -iodo ketones under these conditions proceeded in a moderate to good diastereoselectivity, and the resulted bicyclic cyclopropanols were easily separated by column chromatography over silica gel. exo-7- Isopropylbicyclo[4.1.0]heptan-1-ol obtained in this manner was efficiently employed as a key intermediate in the synthesis of capsaicin. Georg Thieme Verlag Stuttgart - New York.
- Kananovich, Dzmitry G.,Zubrytski, Dzmitry M.,Kulinkovich, Oleg G.
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- Regioselective hydroxylation and dehydrogenation of capsaicin and dihydrocapsaicin by cultured cells of Phytolacca americana
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The biotransformations of capsaicin and dihydrocapsaicin were investigated using cultured plant cells of Phytolacca americana as biocatalysts. Four products, ie 15-hydroxycapsaicin, dihydrocapsaicin, 15-hydroxydihydrocapsaicin, and capsaicin 4-β-glucoside
- Hamada, Hiroki,Ono, Tsubasa,Shimoda, Kei
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p. 103 - 107
(2022/03/18)
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- Aliphatic hydroxylation and epoxidation of capsaicin by cytochrome P450 CYP505X
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Microbial cytochrome P450 enzymes (CYPs) are able to mimic the metabolism of human CYPs. One challenge is to identify the respective drug metabolites and to compare substrate specificities to those of the human enzymes. In this study, a class VIII self-sufficient CYP from Aspergillus fumigatus (CYP505X) and variants of this enzyme were heterologously expressed in E. coli. The substrate scope of the variants was determined using active pharmaceutical ingredients (APIs) and (hetero)cyclic compounds. Capsaicin – the active compound in chili peppers – was oxidized most efficiently (4.36 μM/min) in a whole cell mediated biotransformation. The products were isolated, purified and their structures elucidated by 1D and 2D NMR. The two major metabolites showed modifications on the lipophilic side chain. Specifically, capsaicin was hydroxylated at position 8 to give (E)-8-hydroxy-N-(4-hydroxy-3-methoxybenzyl)-8-methylnon-6-enamide and epoxidized at the double bond to give N-(4-hydroxy-3-methoxybenzyl)-5-(3-isopropyloxiran-2-yl)-pentanamide.
- Migglautsch, Anna K.,Willim, Melissa,Schweda, Bettina,Glieder, Anton,Breinbauer, Rolf,Winkler, Margit
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p. 6199 - 6204
(2018/09/21)
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- Total synthesis of capsaicin analogues from lignin-derived compounds by combined heterogeneous metal, organocatalytic and enzymatic cascades in one pot
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The total synthesis of capsaicin analogues was performed in one pot, starting from compounds that can be derived from lignin. Heterogeneous palladium nanoparticles were used to oxidise alcohols to aldehydes, which were further converted to amines by an enzyme cascade system, including an amine transaminase. It was shown that the palladium catalyst and the enzyme cascade system could be successfully combined in the same pot for conversion of alcohols to amines without any purification of intermediates. The intermediate vanillylamine, prepared with the enzyme cascade system, could be further converted to capsaicin analogues without any purification using either fatty acids and a lipase, or Schotten-Baumann conditions, in the same pot. An aldol compound (a simple lignin model) could also be used as starting material for the synthesis of capsaicin analogues. Using L-alanine as organocatalyst, vanillin could be obtained by a retro-aldol reaction. This could be combined with the enzyme cascade system to convert the aldol compound to vanillylamine in a one-step one-pot reaction.
- Anderson, Mattias,Afewerki, Samson,Berglund, Per,Cordova, Armando
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p. 2113 - 2118
(2014/07/07)
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- [8-[Bis(carboxymethyl)aminomethyl]-6-bromo-7-hydroxycoumarin-4-yl]methyl Moieties as photoremovable protecting groups for compounds with COOH, NH 2, OH, and C-O functions
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We introduce a variant of coumarin-based photoactivatable protecting groups and use it exemplarily for caging of a carboxylic acid, an amine, a phenol, and a carbonyl compound. The caged compounds are efficiently photolyzed at long-wavelength UV/vis irradiation. Compared to the corresponding (6-bromo-7-hydroxycoumarin-4-yl)methyl (Bhc) derivatives, the novel coumarin-type caged compounds are distinguished by (i) dramatically increased solubilities in aqueous buffers, (ii) lower pKa values of the C7 hydroxyl of the coumarin chromophore, thus permitting efficient photorelease at lower pH, and (iii) higher photolysis quantum yields in the case of photoprotected carbonyl compounds. The primary step of the photocleavages occurs with rate constants of about 109 s-1.
- Hagen, Volker,Kilic, Funda,Schaal, Janina,Dekowski, Brigitte,Schmidt, Reinhard,Kotzur, Nico
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scheme or table
p. 2790 - 2797
(2010/08/03)
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- Compounds and compositions for treating infection
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Compounds from 14 Kenyan plants, including from the root of Dovyalis abyssinica and Clutia robusta have been characterized and isolated, and their uses are disclosed.
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- Drug delivery by an enzyme-mediated cyclization of a lipid prodrug with unique bilayer-formation properties
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Special delivery: Liposomal drug-delivery systems in which prodrugs are activated specifically by disease-associated enzymes have great potential for the treatment of severe diseases, such as cancer. A new type of phospholipid-based prodrug has the ability to form stable small unilamellar vesicles (see picture). Activation of the prodrug vesicles by the enzyme sPLA2 initiates a cyclization reaction, which leads to the release of the drug.
- Linderoth, Lars,Peters, Gnther H.,Madsen, Robert,Andresen, Thomas L.
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supporting information; experimental part
p. 1823 - 1826
(2009/09/07)
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- Kavalactone compositions and methods of use
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This invention relates to kavalactone-containing compositions, and more particularly to compositions having compounds derived from kavalactones and from capsaicinoids. The compositions are useful in modulating pain, and thus can be used to mediate, or eliminate, sensations of pain, thereby providing pain relief and reduction.
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- Formulations for the treatment of gastro-oesophageal reflux
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Formulations for the treatment of gastro-oesophageal reflux diseases include a carrier vehicle and an active gastro-protective agent. The carrier vehicle is either capable of forming a floating barrier layer on contact with gastric acid or of forming a bioadhesive film before any contact with gastric acid, so as to protect gastric mucosa from irritation by the gastric acid. A preferred active ingredient is capsaicin. The carrier vehicle preferably contains alginate or cross-linked polyacrylic acid.
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- Method for industrial purification of capsaicin
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The invention provides a method for industrial purification of Capsaicin in high purity from capsinoids (Capsaicin and analogues), more specifically, a method for industrial purification of Capsaicin which comprises contacting capsinoids containing Capsaicin in a hydrophilic solvent with a silver compound in an aqueous solution to form a Capsaicin-silver complex which is soluble in water, and recovering highly pure Capsaicin from the Capsaicin-silver complex without chromatography.
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- A general and stereoselective synthesis of the capsaicinoids via the orthoester Claisen rearrangement
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Capsaicin, a main pungent principle of hot pepper, and its 15 analogs have been efficiently synthesized. The key step of this synthetic scheme is the orthoester Claisen rearrangement, which transformed allylic alcohols 2A-C to (E)-alkenoates 3A-C (E/Z > 100) in a highly stereoselective manner. The subsequent carbon chain elongations on 3 based on the cyanation or the malonic acid ester synthesis afforded (E)-alkenoic acids 8, which were converted to the corresponding acid chloride and then coupled with vanillylamine to give capsaicinoids. HPLC and CE (capillary electrophoresis) analyses of these capsaicinoids were also carried out.
- Kaga, Harumi,Goto, Kouhei,Takahashi, Tomiki,Hino, Masao,Tokuhashi, Takashi,Orito, Kazuhiko
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p. 8451 - 8470
(2007/10/03)
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- Microcapsules containing capsaicine compound and their production
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The present invention provides a resin molding composition for preventing gnawing damage by the animal, a microcapsule filled with a capsaicine compound, and a process for producing the capsaicine compound and the microcapsule.
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- Glycosylation of Capsaicin by Cell Suspension cultures of Coffea arabica
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Capsaicin was converted into the corresponding glycoside when administered to cell suspension cultures of Coffea arabica cultured in a modified Murashige and Skoog's medium with 5 μM 2,4-dichlorophenoxyacetic acid and 0.5 μM kinetin.The glucoside was identified as capsaicin-β-D-glucopyranoside by FAB-MS. 1H-NMR, and hydrolysis with α- and β-glucosidases.The pungency of the glucoside was approximately 1/100 of that of capsaicin.
- Kometani, Takashi,Tanimoto, Hidenori,Nishimura, Takahisa,Kanbara, Isao,Okada, Shigetaka
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p. 2192 - 2193
(2007/10/02)
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- An Alternate Synthesis of the Capsaicinoids
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Five capsaicinoids, the pungent ingredients of hot peppers, have been efficiently synthesized by a method involving the Wittig reaction between isobutyl triphenylphosphorane and the appropriate lactols (3), followed by the nitrous acid-induced isomerization of the resultant (Z)-olefins (4) to (E)-olefins (5).
- Kaga, Harumi,Goto, Kouhei,Fukuda, Takashi,Orito, Kazuhiko
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p. 946 - 948
(2007/10/02)
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- The Capsaicinoids: Their Separation, Synthesis, and Mutagenicity
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Capsaicin (1b), the pungent ingredient in many varietes of Capsicums has recently been implicated as a possible carcinogen.When obtained from natural sources 1b is always accompanied by a number of related homologues.We have isolated seven of these homologues, characterized them, and synthesized them by a general and unique route developed in our laboratories.Also reported are mutagenicity data for 1b and an extract of red pepper as measured by the Ames assay and the V-79 mammalian cell assay.
- Gannett, Peter M.,Nagel, Donald L.,Reilly, Pam J.,Lawson, Terence,Sharpe, Jody,Toth, Bela
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p. 1064 - 1071
(2007/10/02)
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