- 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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Page/Page column 126
(2021/05/15)
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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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supporting information
p. 11802 - 11806
(2018/09/10)
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- N-GLYCOSYLATION OF PEPTIDES AND PROTEINS
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A process for the production of a glycoconjugate by N-glycosylation of a protein or peptide comprising the sequence D/E-X-N-X-S/T, wherein each X is the same or different and is any natural amino acid other than proline, wherein the process comprises reacting the protein or peptide with a polyisoprenyl pyrophosphate of formula (I), or a salt thereof, in the presence of PglB: (I) to produce the glycoconjugate comprising the protein or peptide having a saccharide [SI] linked to the asparagine in the sequence D/E-X-N-X-S/T. Polyisoprenylpyrophosphates used as substrates in the biocatalytic process are also provided, as well as certain glycoconjugates.
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Page/Page column 18
(2015/05/05)
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- Rationally designed short polyisoprenol-linked PglB substrates for engineered polypeptide and protein N-glycosylation
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The lipid carrier specificity of the protein N-glycosylation enzyme C. jejuni PglB was tested using a logical, synthetic array of natural and unnatural C10, C20, C30, and C40 polyisoprenol sugar pyrophosphates, including those bearing repeating cis-prenyl units. Unusual, short, synthetically accessible C20 prenols (nerylnerol 1d and geranylnerol 1e) were shown to be effective lipid carriers for PglB sugar substrates. Kinetic analyses for PglB revealed clear KM-only modulation with lipid chain length, thereby implicating successful in vitro application at appropriate concentrations. This was confirmed by optimized, efficient in vitro synthesis allowing >90% of Asn-linked β-N-GlcNAc-ylated peptide and proteins. This reveals a simple, flexible biocatalytic method for glycoconjugate synthesis using PglB N-glycosylation machinery and varied chemically synthesized glycosylation donor precursors.
- Liu, Feng,Vijayakrishnan, Balakumar,Faridmoayer, Amirreza,Taylor, Thomas A.,Parsons, Thomas B.,Bernardes, Goncalo J.L.,Kowarik, Michael,Davis, Benjamin G.
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supporting information
p. 566 - 569
(2014/02/14)
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- Synthesis of isotopically labelled oligoprenyl diphosphates and their application in mechanistic investigations of terpene cyclases
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A flexible, efficient and robust method for the synthesis of isotopically labelled oligoprenyl diphosphates was developed. The method makes use of just a few building blocks (acetone, triethyl phosphonoacetate, and ethyl acetoacetate) from which several i
- Citron, Christian A.,Rabe, Patrick,Barra, Lena,Nakano, Chiaki,Hoshino, Tsutomu,Dickschat, Jeroen S.
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p. 7684 - 7691
(2015/04/22)
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- Total synthesis of cristatic acid based on late-stage decarboxylative allylic migration and biomimetic aromatization of a diketo dioxinone
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A fifteen-step synthesis of methyl cristatate is described. tert-Butyl-[(E)-6-iodo-3-methylhex-2-enyloxy)]diphenylsilane, synthesized from geraniol, was coupled with 2-(diethoxymethyl)-4-lithiofuran and transformed - by acetal hydrolysis, Wittig olefinati
- George, Nicolas S.,Anderson, Katie E.,Barrett, Anthony G. M.
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p. 7604 - 7610
(2013/12/04)
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- Biomimetic cyclization of epoxide precursors of indole mono-, sesquiand diterpene alkaloids by lewis acids
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Cyclization of the synthesized epoxide precursors of indole mono-, sesqui- and diterpene alkaloids was performed to elucidate the mechanism for biomimetic cationic cyclization to polycyclic structures. 3-(6,7- Epoxygeranyl)indole (11), 3-(10,11-epoxyfarne
- Isaka, Tetsuya,Hasegawa, Morifumi,Toshima, Hiroaki
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experimental part
p. 2213 - 2222
(2012/02/14)
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- Synthesis of moenocinol and its analogs using BT-sulfone in Julia-Kocienski olefination
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Moenocinol (C25H42O), the acyclic terpenoid unsaturated lipid part of moenomycin antibiotics, was prepared by an expedient method, which comprised organometallic reaction, Julia-Kocienski olefination, and enolate carbon bond formation as the key steps. The starting materials, nerol and 3-butyn-1-ol, were elaborated to the benzothiazole sulfone 2 and aldehyde 3, and the subsequent Julia-Kocienski olefination occurred in a stereospecific manner to give the desired 6E-configuration of moenocinol. Moenocinol (1) was thus synthesized by 10 linear steps in 12% overall yield, and its analogs 23, 24, and 28 with different chain lengths and unsaturation degrees were also realized by the similar reaction sequences.
- Huang, Hung-Jyun,Yang, Wen-Bin
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p. 1429 - 1433
(2008/02/02)
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- Stereoselective disposition of the geminal dimethyl group in the cyclization of geranyl acetate under zeolite confinement conditions
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The stereochemistry in the acid-catalysed biomimetic cyclization of [8,8,8-D3]geranyl acetate was examined in solution and under conditions of zeolite Y confinement. In the intrazeolite reaction the gem-allylic methyl group adopts a diastereose
- Tsangarakis, Constantinos,Stratakis, Manolis
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p. 4435 - 4439
(2007/10/03)
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- Development of a concise and diversity-oriented approach for the synthesis of plecomacrolides via the diene-ene RCM
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A concise synthesis of the core structures of plecomacrolide with ring sizes varying from 16 to 19 atoms was achieved for the first time by the diene-ene ring-closing olefin metathesis reaction. This approach should allow access to the structurally divers
- Lu, Kui,Huang, Mengwei,Xiang, Zheng,Liu, Yongxiang,Chen, Jiahua,Yang, Zhen
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p. 1193 - 1196
(2007/10/03)
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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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- Pheromone synthesis, CXCVI. Synthesis of germacrene-B and its extension to the synthesis of (±)-9-methylgermacrene-B, the racemate of the male- produced sex pheromone of the sandfly Lutzomyia longipalpis from Lapinha, Brazil
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Both germacrene-B (2) and 9-methylgermacrene-B [(±)-1] were synthesized by employing cyclization reactions [8 → 9 and (±)-20 → (±)-21] as the key steps. The latter [(±)-1] was shown to be the racemate of the male-produced sex pheromone of the sandfly Lutz
- Muto, Shin-Etsu,Nishimura, Yutaka,Mori, Kenji
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p. 2159 - 2165
(2007/10/03)
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- Synthesis of tricyclopolyprenols via a radical addition and a stereoselective elimination, part II: (Z)-tricyclopentaprenol, (E,E)- and (Z,Z)-tricyclohexaprenol, (Z,Z,Z)-tricycloheptaprenol
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Four tricyclopolyprenols have been synthesised by addition of the isocopalenyl radical either to a 2-methylene-3-hydroxy alkenenitrile (in the case of (E,E)-tricyclohexaprenol) or to a methyl 2-methylene-3-hydroxy alkenoate (in the case of the three (Z)-t
- Jenn, Thierry,Heissler, Denis
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p. 107 - 118
(2007/10/03)
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- Farnesyl-diphosphate synthase. Catalysis of an intramolecular prenyl transfer with bisubstrate analogs
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Bisubstrate analogs for isopentenyl diphosphate and dimethylallyl diphosphate were examined as substrates for farnesyl-diphosphate synthase. The hydrocarbon moieties of the normal substrates were joined by a one-carbon bridge that permits reaction between
- Jo Davisson,Neal, Timothy R.,Dale Poulter
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p. 1235 - 1245
(2007/10/02)
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