- BIOSYNTHESIS OF CHEMICALLY DIVERSIFIED NON-NATURAL TERPENE PRODUCTS
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The disclosure relates to compounds of the formulae (l)-(IV) and their use as substrates for making terpenoids. New substrates for terpene biosynthesis and methods for making new types of terpenes are described herein. Diterpenes occupy a unique molecular
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- Exploiting the Synthetic Potential of Sesquiterpene Cyclases for Generating Unnatural Terpenoids
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The substrate flexibility of eight purified sesquiterpene cyclases was evaluated using six new heteroatom-modified farnesyl pyrophosphates, and the formation of six new heteroatom-modified macrocyclic and tricyclic sesquiterpenoids is described. GC-O analysis revealed that tricyclic tetrahydrofuran exhibits an ethereal, peppery, and camphor-like olfactoric scent.
- Oberhauser, Clara,Harms, Vanessa,Seidel, Katja,Schr?der, Benjamin,Ekramzadeh, Kimia,Beutel, Sascha,Winkler, Sven,Lauterbach, Lukas,Dickschat, Jeroen S.,Kirschning, Andreas
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p. 11802 - 11806
(2018/09/10)
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- Substrate specificities of E- and Z-farnesyl diphosphate synthases with substrate analogs
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Prenyltransferases catalyzes the basic isoprenoid chain elongation to produce prenyl diphosphates, which led to upward of 30,000 diverse isoprenoids as steroids, carotenoids, natural rubbers, and prenyl proteins. Here, we determined the reactivities of E- and Z-farnesyl diphosphate synthases (E- and Z-FPP synthases) isolated from Bacillus stearothermophilus and Thermobifida fusca, respectively. For this purpose we use the synthetic substrate analogs, 8-tetrahydropyran-2-yloxy-, 8-hydroxy- and 8-acetoxygeranyl diphosphates. Z-FPP synthase catalyzed the reaction between 8-hydroxygeranyl diphosphate (HOGPP) and isopentenyl diphosphate (IPP), which produced (2Z)-12-hydroxyfarnesyl diphosphate (yield: 16.7%) and (2Z, 6Z)-16-hydroxygeranylgeranyl diphosphate (yield: 6.6%). Neither E- nor Z-farnesyl diphosphate synthases detectably catalyzed reactions between 8-tetrahydropyran-2-yloxygeranyl diphosphate (8-THPOGPP) and IPP. However, a mutated E-FPP synthase (Y81S), did catalyze this reaction, producing 12-tetrahydropyran-2-yloxyfarnesyl diphosphate (12-THPOFPP) with a yield of 12.3%. Wild-type E-FPP synthase catalyzed the reaction of 8-acetoxygeranyl diphosphate (8-AcOGPP) with IPP, which produced 12-acetoxyfarnesyl diphosphate (12-AcOFPP) (yield, 21.8%). Mutant E-FPP synthase catalyzed the reaction between 8-AcOGPP with IPP, producing 12-AcOFPP and 16-acetoxygeranylgeranyl diphosphate (16-AcOGGPP) with respective yields of 55.3% and 1.7%. We believe our results contribute to a better understanding of the catalytic properties of these key enzymes and illustrate their use in the stereo-specific syntheses of compounds that may have significant biotechnological and medical applications.
- Nagaki, Masahiko,Ichijo, Takumi,Kobashi, Rikiya,Yagihashi, Yusuke,Musashi, Tohru,Kawakami, Jun,Ohya, Norimasa,Gotoh, Takeshi,Sagami, Hiroshi
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experimental part
p. 1 - 6
(2012/09/05)
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- Alkene substituents for selective activation of endo-regioselective polyepoxide oxacyclizations
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(Chemical equation presented) The presence of an alkenyl substituent on the terminal epoxide of a polyepoxide substrate enhances the yield of all-endo-regioselective tandem oxacyclization to trans-syn-trans-fused polycyclic ethers. For a substrate in which the epoxide and alkene functional groups are separated by two methylene substituents, a novel bromonium ion-induced endo-regioselective cyclization to bromooxepane is also described.
- Bravo, Fernando,McDonald, Frank E.,Neiwert, Wade A.,Hardcastle, Kenneth I.
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p. 4487 - 4489
(2007/10/03)
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- Selenium dioxide E-methyl oxidation of suitably protected geranyl derivatives - Synthesis of farnesyl mimics
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Difunctional allylic terpenes are important synthetic building blocks. Functionalisation of protected geranyl derivatives by SeO2 provides a convenient route to such compounds. The effect of the geranyl protecting group on the oxidation of the
- Fairlamb, Ian J.S.,Dickinson, Julia M.,Pegg, Mathew
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p. 2205 - 2208
(2007/10/03)
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- Stereoselective synthesis of the S- and Y-ring systems of maitotoxin
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The seven-membered S- and Y-ring systems of maitotoxin (1) were stereoselectively synthesized based on the rearrangement-ring expansion of the six-membered ethers having the mesylate group on the α-side chain.
- Nakata,Nomura,Matsukura
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p. 627 - 629
(2007/10/03)
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