- 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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supporting information
p. 2113 - 2118
(2014/07/07)
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- 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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scheme or table
p. 1043 - 1046
(2010/06/14)
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- Application of hansch's model to capsaicinoids and capsinoids: A study using the quantitative structure-activity relationship. A novel method for the synthesis of capsinoids
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We describe a synthetic approach for two families of compounds, the capsaicinoids and capsinoids, as part of a study of the quantitative relationship between structure and activity. A total of 14 capsaicinoids of increasing lateral chain lengths, from 2 to 16 carbon atoms, were synthesized. In addition, 14 capsinoids with identical lateral chains, as well as capsiate and dihydrocapsiate, have been synthesized, and a new method for the synthesis of these compounds has been developed. The yields range from 48.35 to 98.98%. It has been found that the synthetic capsaicinoids and capsinoids present a lipophilia similar to those of the natural compounds and present similar biological activity. The bioactivity of the synthetic capsaicinoids and capsinoids decreases proportionally to the degree of difference in lipophilia (higher or lower) compared to the natural compounds. Biological activity was determined using the etiolated wheat (Triticum aestlvum L.) coleoptiles bioassay and by comparing results of the synthesis with those presented by their counterpart natural compounds. The bioactivities found correlated directly to the lipophilic properties of the synthesized compounds.
- Barbero, Gerardo F.,Molinillo, Jose M. G.,Varela, Rosa M.,Palma, Miguel,MacIas, Francisco A.,Barroso, Carmelo G.
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experimental part
p. 3342 - 3349
(2011/07/30)
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- Synthesis and elucidation of deuterated vanillylamine hydrochloride and capsaicin
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Capsaicin is the major pungent component of hot peppers, which belong to the plant genus Capsicum. Although the biosynthesis of capsaicin is known to involve the condensation of vanillylamine and 8-methylnonenoic acid by capsaicin synthase, the mechanism of biosynthesis is still not fully understood. In this study, deuterium labelled versions of capsaicin and the precursor vanillylamine were synthesized in order to investigate the biosynthesis of capsaicin in hot peppers. Copyright
- Kim, Sang Wook,Park, Jeong Hoon,Jung, Soon Jae,Choi, Tae Bum,Hur, Min Goo,Yang, Seung Dae,Yu, Kook Hyun
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experimental part
p. 563 - 565
(2010/07/02)
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- Chili pepper fruits: Presumed precursors of fatty acids characteristic for capsaicinoids
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Capsaicin is a molecule unique to fruits from the genus Capsicum. It is responsible for the pungent sensation and displays valuable pharmacological properties. Despite the fruits' economic importance and decades of research, the regulation of the content of capsaicinoids in individual fruits is not completely elucidated, and no agricultural cultivation of chili of defined pungency is assured. Precursor candidates of the fatty acid moiety of the capsaicinoids, especially for the unique 8-methyl-trans-6-nonenoic acid, were examined. Thioesters, acyl-ACP and acyl-CoA, were isolated from the placenta of Capsicum fruits by means of DEAE-Sepharose chromatography, selectively converted to the corresponding N-butylamides, and analyzed by GC-MS. Fatty acid moieties characteristic for capsaicinoids were identified. In two different varieties (Capsicum chinense var. Habanero orange and Capsicum annuum var. Jalapeno) it was shown that the fatty acid pattern corresponds to the distribution pattern of the capsaicinoids formed up to this time. The acyl-thioester fractions contained already the 8-methyl-trans-6-nonenoic acid.
- Thiele, Roland,Mueller-Seitz, Erika,Petz, Michael
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experimental part
p. 4219 - 4224
(2010/03/31)
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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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- 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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