- Stereospecific synthesis and biological evaluation of farnesyl diphosphate isomers
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(Matrix presented) A unified, stereospecific synthetic route to the three geometric isomers of (E,E)-farnesyl diphosphate (E,E-FPP) (1,2, and 3) has been developed. The key feature of this synthesis is the ability to control the stereochemistry of triflation of the β-ketoester 10 to give either 11 or 14. Preliminary evaluation of these compounds with protein-farnesyl transferase indicates that 1 and 2 are surprisingly effective substrates; however, Z,Z-FPP (3) is a poor substrate and a sub-micromolar inhibitor.
- Shao, Ying,Eummer, Jeffrey T.,Gibbs, Richard A.
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Read Online
- PRODUCTION OF FARNESOL
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The present invention relates to an improved way for the production of farnesol.
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Page/Page column 11
(2017/04/11)
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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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- Method for Converting Farnesol to Nerolidol in the Presence of Alpha-Bisabolol
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A method for converting farnesol to nerolidol in the presence of alpha-bisabolol including providing or preparing a mixture of alpha-bisabolol, farnesol, and one or more catalysts for selective isomerization of farnesol to nerolidol in the presence of alpha-bisabolol, and converting at least a portion of the farnesol to nerolidol.
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- UNIQUE HALOGEN-INDUCED CYCLIZATIONS, REAGENTS THEREFOR, AND COMPOUNDS PRODUCED THEREBY
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This disclosure is related to halonium compounds useful for cyclization of polyenes, alkenoic acids, and alkenyl alkyl ethers, and halogenation of aromatic compounds. The synthesis of such halonium compounds, compounds made using such halonium compounds, and synthesis of natural compounds, including decalins, using the halonium compounds is also disclosed. A representative halonium compound of the disclosure is: Formula (I).
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- Simple reagents for direct halonium-induced polyene cyclizations
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Although there are many reagent combinations that can initiate polyene cyclizations, simple electrophilic halogen sources have not yet proven broadly effective as promoters of such processes. Herein is described a readily prepared and stable class of reagents capable of effecting such transformations for a wide range of electron-rich and -deficient terpenes derived from geraniol, farnesol, and nerol, thereby enabling the effective synthesis of a diverse array of complex chlorine-, bromine-, and iodine-containing polycyclic frameworks. Efforts to date have led to the first racemic laboratory total synthesis and structural revision of the anti-HIV natural product peyssonol A as well as an efficient and concise inaugural total synthesis of peyssonoic acid A. They have also permitted formal racemic total syntheses of aplysin-20, loliolide, K-76, and stemodin to be achieved through routes that are typically shorter, higher-yielding, and more environmentally conscious than previous efforts. Preliminary attempts to use chiral forms of the reagent class for enantioselective alkene halogenation are also described.
- Snyder, Scott A.,Treitler, Daniel S.,Brucks, Alexandria P.
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supporting information; experimental part
p. 14303 - 14314
(2011/01/04)
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- Synthesis of farnesol isomers via a modified wittig procedure
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(Chemical Equation Presented) The four olefin stereoisomers of farnesol have been synthesized from readily available nerylacetone or commercial geranylacetone. A new variation on the use of β-oxido ylides favored the (2Z)-stereoisomers, whereas the (2E)-isomers were obtained through a classical Horner-Wadsworth-Emmons condensation with triethyl phosphonoacetate and reduction of the resulting ester.
- Yu, Jose S.,Kleckley, Troy S.,Wiemer, David F.
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p. 4803 - 4806
(2007/10/03)
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- Composition, method, and apparatus to attract bees
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Applicant's invention includes an improved bee attracting composition. Applicant's invention further includes a bee attracting device formed from his improved bee attracting composition. Applicant's bee attracting device can be further coated with a second bee attracting composition. Applicant's invention further includes a method and apparatus for attracting and immobilizing bees using a substrate coated with an adhesive composition upon which Applicant's bee attracting composition is disposed.
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- A novel, highly selective, and general methodology for the synthesis of 1,5-diene-containing oligoisoprenoids of all possible geometrical combinations exemplified by an iterative and convergent synthesis of coenzyme Q10
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Chemical equation presented A truly general, versatile, and highly regio- and stereoselective methodology for the synthesis of terpenoids containing 1,5-diene units of E and/or Z geometry critically involves Pd-catalyzed homoallyl- and homopropargyl-alkenyl coupling and Zr-catalyzed carboalumination of alkynes. By using this methodology, coenzyme Q10, (E,Z,E)-geranylgeranoil, and other natural or unnatural compounds have been synthesized efficiently.
- Negishi, Ei-Ichi,Liou, Show-Yee,Xu, Caiding,Huo, Shouquan
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p. 261 - 264
(2007/10/03)
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- Synthesis and biological evaluation of the geometric farnesylated analogues of the a-factor mating peptide of Saccharomyces cerevisiae
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The a-factor of Saccharomyces cerevisiae is a dodecapeptide pheromone (YIIKGVFWDPAC-(Farnesyl)-OCH3, 1), in which post-translational modification with a farnesyl isoprenoid and carboxymethyl group is required for full biological activity. This peptide has been used as a model system to explore the biological function of the farnesylcysteine moiety, which is found on and required for the biological activity of many key mammalian proteins. The objective of this particular study was the determination of the biological effect of double bond isomerization of the natural E,E-farnesyl moiety on the biological activity of the a-factor. A unified, stereoselective synthetic route to the three geometric isomers of E,E-farnesol (12, 13, and 14) has been developed. The key feature of this synthesis is the ability to control the stereochemistry of triflation of the β-ketoester 22 to give either 23 or 25. The three farnesol isomers were converted to the corresponding isomeric a-factors (9, 10 and 11) via a modified version of a previously utilized synthetic route. Biological evaluation of these peptides indicates that, surprisingly, all three possess nearly equivalent activity to the natural a-factor bearing the E,E-farnesyl moiety.
- Xie,Shao,Becker,Naider,Gibbs
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p. 8552 - 8563
(2007/10/03)
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- Z-Stereoselective Peterson olefination of ketones
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A highly-stereoselective method (90percent of the Z-isomer) was developed for the Peterson olefination of ketones with nerylacetone (1) as an example.The method is based on the introduction of a PhS group, which is removed after completion of the reaction, at the ketone C(3) atom. - Keywords: olefination of ketones, stereoselective synthesis, Peterson reaction, 2Z- and 2E-4-phenylthiofarnesoles and 2Z- and 2E-4-phenylthiofarnesoates
- Grigorieva, N. Ya.,Pinsker, O. A.,Buevich, A. V.,Moiseenkov, A. M.
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p. 492 - 499
(2007/10/02)
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- STEREOSELECTIVE SYNTHESIS OF A CISOID C10 ISOPRENOID BUILDING BLOCK AND SOME ALL-CIS-POLYPRENOLS
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As the key compound for the construction of cisoid terpenoids, (2Z,6Z)-8-benzyloxy-1-chloro-2,6-dimethylocta-2,6-diene was sinthesized stereoselectively via the Wittig reaction starting from nerol.The ten-carbon building block was coupled with prenyl or neryl p-tolyl sulfone to afford, after reductive desulfonylation, (Z,Z)-farnesol and (Z,Z,Z)-nerylnerol, respectively.
- Sato, Kikumasa,Miyamoto, Osamu,Inoue, Seiichi,Furusawa, Fumio,Matsuhashi, Yasusuke
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p. 725 - 728
(2007/10/02)
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- Sur la stereochimie de la cyclisation du nerolidol an α-bisabolol
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The cyclisation of linalyl to α-terpinyl derivatives is known to take place with efficient transfer of chirality.Information was needed about the analogous cyclisation of nerolidyl to bisabolyl derivatives.This was made possible through the recent determination of the absolute configuration of bisabolol and epibisabolol.Hydrolysis of (+)(S) nerolidyl paranitrobenzoate has been carried out under the experimental conditons used for (-)(R) linalyl paranitrobenzoate.Strong asymmetric induction was observed about C4 (in the ring) but very little, if any, about C8 (in the chain).The cyclisation of (+)(S) nerolidol has been brought about by 90/10 aqueous formic acid.Under these experimental conditions very little asymmetric induction is observed about C8 or C4.This is explained by rapid racemisation of the starting material under the cyclisation conditions.
- Fourneron, Jean-Dominique,Julia, Marc
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p. 387 - 392
(2007/10/02)
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- Allyl acetyl derivatives of β, γ-unsaturated aldehyde
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An unsaturated carbonyl compound, for example, one expressed by the following formula, STR1 is prepared by maintaining at an elevated temperature a novel allyl acetal of a β,γ-unsaturated aldehyde, for example, one expressed by the following formula STR2 The allyl acetal can be derived, for example, for 3-methyl-3-butenal-1 having 5 carbon atoms and prenyl alcohol having 5 carbon atoms. Thus, the unsaturated aldehyde having the increased number of carbon atoms can be formed in a high yield by a relatively simple reaction.
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