- Structural and functional analysis of bacillus subtilis yisp reveals a role of its product in biofilm production
-
YisP is involved in biofilm formation in Bacillus subtilis and has been predicted to produce C30 isoprenoids. We determined the structure of YisP and observed that it adopts the same fold as squalene and dehydrosqualene synthases. However, the first aspartate-rich motif found in essentially all isoprenoid synthases is aspartate poor in YisP and cannot catalyze head-to-head condensation reactions. We find that YisP acts as a phosphatase, catalyzing formation of farnesol from farnesyl diphosphate, and that it is the first phosphatase to adopt the fold seen in the head-to-head prenyl synthases. Farnesol restores biofilm formation in a Δyisp mutant and modifies lipid membrane structure similarly to the virulence factor staphyloxanthin. This work clarifies the role of YisP in biofilm formation and suggests an intriguing possibility that many of the YisP-like homologs found in other bacteria may also have interesting products and functions.
- Feng, Xinxin,Hu, Yumei,Zheng, Yingying,Zhu, Wei,Li, Kai,Huang, Chun-Hsiang,Ko, Tzu-Ping,Ren, Feifei,Chan, Hsiu-Chien,Nega, Mulugeta,Bogue, Shannon,Lpez, Daniel,Kolter, Roberto,G?tz, Friedrich,Guo, Rey-Ting,Oldfield, Eric
-
-
Read Online
- Synthesis and biological evaluation of farnesylthiosalicylamides as potential anti-tumor agents
-
Fourteen hybrids of farnesylthiosalicylic acid (FTS) with various diamines were synthesized and biologically evaluated. It was found that FTS-monoamide molecules (10a-g) displayed strong anti-proliferative activity against seven human cancer cell lines, superior to FTS and FTS-bisamide compounds (11a-g). The mono-amide 10f was the most active, with IC50s of 3.78-7.63 μM against all tested cancer cells, even more potent than sorafenib (9.12-22.9 μM). In addition, 10f induced SMMC-7721 cell apoptosis, down-regulated the expression of Bcl-2 and up-regulated Bax and caspase-3. Furthermore, 10f had the improved aqueous solubility relative to FTS. Finally, treatment with 10f dose-dependently inhibited the Ras-related signaling pathways in SMMC-7721 cells. Collectively, 10f could be a promising candidate for the intervention of human cancers.
- Ling, Yong,Wang, Zhiqiang,Zhu, Hongyan,Wang, Xuemin,Zhang, Wei,Wang, Xinyang,Chen, Li,Huang, Zhangjian,Zhang, Yihua
-
-
Read Online
- Molecular cloning and characterization of drimenol synthase from valerian plant (Valeriana officinalis)
-
Drimenol, a sesquiterpene alcohol, and its derivatives display diverse bio-activities in nature. However, a drimenol synthase gene has yet to be identified. We identified a new sesquiterpene synthase cDNA (VoTPS3) in valerian plant (Valeriana officinalis). Purification and NMR analyses of the VoTPS3-produced terpene, and characterization of the VoTPS3 enzyme confirmed that VoTPS3 synthesizes (-)-drimenol. In feeding assays, possible reaction intermediates, farnesol and drimenyl diphosphate, could not be converted to drimenol, suggesting that the intermediate remains tightly bound to VoTPS3 during catalysis. A mechanistic consideration of (-)-drimenol synthesis suggests that drimenol synthase is likely to use a protonation-initiated cyclization, which is rare for sesquiterpene synthases. VoTPS3 can be used to produce (-)-drimenol, from which useful drimane-type terpenes can be synthesized.
- Kwon, Moonhyuk,Cochrane, Stephen A.,Vederas, John C.,Ro, Dae-Kyun
-
-
Read Online
- Roles of rat and human aldo-keto reductases in metabolism of farnesol and geranylgeraniol
-
Farnesol (FOH) and geranylgeraniol (GGOH) with multiple biological actions are produced from the mevalonate pathway, and catabolized into farnesoic acid and geranylgeranoic acid, respectively, via the aldehyde intermediates (farnesal and geranylgeranial). We investigated the intracellular distribution, sequences and properties of the oxidoreductases responsible for the metabolic steps in rat tissues. The oxidation of FOH and GGOH into their aldehyde intermediates were mainly mediated by alcohol dehydrogenases 1 (in the liver and colon) and 7 (in the stomach and lung), and the subsequent step into the carboxylic acids was catalyzed by a microsomal aldehyde dehydrogenase. In addition, high reductase activity catalyzing the aldehyde intermediates into FOH (or GGOH) was detected in the cytosols of the extra-hepatic tissues, where the major reductase was identified as aldo-keto reductase (AKR) 1C15. Human reductases with similar specificity were identified as AKR1B10 and AKR1C3, which most efficiently reduced farnesal and geranylgeranial among seven enzymes in the AKR1A-1C subfamilies. The overall metabolism from FOH to farnesoic acid in cultured cells was significantly decreased by overexpression of AKR1C15, and increased by addition of AKR1C3 inhibitors, tolfenamic acid and R-flurbiprofen. Thus, AKRs (1C15 in rats, and 1B10 and 1C3 in humans) may play an important role in controlling the bioavailability of FOH and GGOH.
- Endo, Satoshi,Matsunaga, Toshiyuki,Ohta, Chisato,Soda, Midori,Kanamori, Ayano,Kitade, Yukio,Ohno, Satoshi,Tajima, Kazuo,El-Kabbani, Ossama,Hara, Akira
-
-
Read Online
- Substrate specificities of E- and Z-farnesyl diphosphate synthases with substrate analogs
-
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
-
-
Read Online
- Biosynthesis of sesterterpenes, head-to-tail triterpenes, and sesquarterpenes in Bacillus clausii: Identification of multifunctional enzymes and analysis of isoprenoid metabolites
-
We performed functional analysis of recombinant enzymes and analysis of isoprenoid metabolites in Bacillus clausii to gain insights into the biosynthesis of rare terpenoid groups of sesterterpenes, head-to-tail triterpenes, and sesquarterpenes. We have identified an (all-E)-isoprenyl diphosphate synthase (E-IDS) homologue as a trifunctional geranylfarnesyl diphosphate (GFPP)/hexaprenyl diphosphate (HexPP)/heptaprenyl diphosphate (HepPP) synthase. In addition, we have redefined the function of a tetraprenyl-β-curcumene synthase homologue as that of a trifunctional sesterterpene/triterpene/sesquarterpene synthase. This study has revealed that GFPP, HexPP, and HepPP, intermediates of two isoprenoid pathways (acyclic terpenes and menaquinones), are biosynthesized by one trifunctional E-IDS. In addition, GFPP/HexPP and HepPP are the primary substrates for the biosynthesis of acyclic terpenes and menaquinone-7, respectively. Multifunctional terpene biosynthetic enzymes: Geranylfarnesyl diphosphate (GFPP), hexaprenyl diphosphate (HexPP), and heptaprenyl diphosphate (HepPP) are intermediates in two isoprenoid pathways and are biosynthesized by one trifunctional (all-E)-isoprenyl diphosphate synthase. GFPP/HexPP and HepPP are mainly utilized for the biosynthesis of acyclic terpenes and menaquinone-7, respectively.
- Ueda, Daijiro,Yamaga, Hiroaki,Murakami, Mizuki,Totsuka, Yusuke,Shinada, Tetsuro,Sato, Tsutomu
-
-
Read Online
- Regiospecific Synthesis of Calcium-Independent Daptomycin Antibiotics using a Chemoenzymatic Method
-
Daptomycin (DAP) is a calcium (Ca2+)-dependent FDA-approved antibiotic drug for the treatment of Gram-positive infections. It possesses a complex pharmacophore hampering derivatization and/or synthesis of analogues. To mimic the Ca2+-binding effect, we used a chemoenzymatic approach to modify the tryptophan (Trp) residue of DAP and synthesize kinetically characterized and structurally elucidated regiospecific Trp-modified DAP analogues. We demonstrated that the modified DAPs are several times more active than the parent molecule against antibiotic-susceptible and antibiotic-resistant Gram-positive bacteria. Strikingly, and in contrast to the parent molecule, the DAP derivatives do not rely on calcium or any additional elements for activity.
- Mupparapu, Nagaraju,Lin, Yu-Hsin Cindy,Kim, Tae Ho,Elshahawi, Sherif I.
-
supporting information
p. 4176 - 4182
(2021/02/01)
-
- SYNTHESIS OF E,E-FARNESOL, FARNESYL ACETATE AND SQUALENE FROM FARNESENE VIA FARNESYL CHLORIDE
-
The present disclosure provides methods for preparing polyunsaturated hydrocarbons, such as E,E-farnesol, farnesyl acetate and squalene, by base catalyzed addition of a dialkylamine to a 3-methylene-1-alkene, such as farnesene. The present disclosure also provides compositions including one more farnesene derivatives prepared using the disclosed methods.
- -
-
Paragraph 0084; 0085
(2019/12/28)
-
- METHOD FOR PRODUCING CARBOXYLIC ACID PRENYL AND PRENOL
-
PROBLEM TO BE SOLVED: To provide a method for producing carboxylic acid prenyls and prenols in high yields and in an industrial and economical advantageous manner. SOLUTION: A production method includes reacting a prenyl amine represented by formula (1), in the presence of a halide, with a carboxylic acid anhydride represented by formula (2), to produce a carboxylic acid prenyl represented by formula (3), and further subjecting the carboxylic acid prenyl to solvolysis, to obtain a prenol represented by formula (6). SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
- -
-
Paragraph 0086-0099
(2019/12/31)
-
- Structure-Function Studies of Artemisia tridentata Farnesyl Diphosphate Synthase and Chrysanthemyl Diphosphate Synthase by Site-Directed Mutagenesis and Morphogenesis
-
The amino acid sequences of farnesyl diphosphate synthase (FPPase) and chrysanthemyl diphosphate synthase (CPPase) from Artemisia tridentata ssp. Spiciformis, minus their chloroplast targeting regions, are 71% identical and 90% similar. FPPase efficiently and selectively synthesizes the "regular" sesquiterpenoid farnesyl diphosphate (FPP) by coupling isopentenyl diphosphate (IPP) to dimethylallyl diphosphate (DMAPP) and then to geranyl diphosphate (GPP). In contrast, CPPase is an inefficient promiscuous enzyme, which synthesizes the "irregular" monoterpenes chrysanthemyl diphosphate (CPP), lavandulyl diphosphate (LPP), and trace quantities of maconelliyl diphosphate (MPP) from two molecules of DMAPP, and couples IPP to DMAPP to give GPP. A. tridentata FPPase and CPPase belong to the chain elongation protein family (PF00348), a subgroup of the terpenoid synthase superfamily (CL0613) whose members have a characteristic α terpene synthase α-helical fold. The active sites of A. tridentata FPPase and CPPase are located within a six-helix bundle containing amino acids 53 to 241. The two enzymes were metamorphosed into one another by sequentially replacing the loops and helices of the six-helix bundle from enzyme with those from the other. Chain elongation was the dominant activity during the N-terminal to C-terminal metamorphosis of FPPase to CPPase, with product selectivity gradually switching from FPP to GPP, until replacement of the final α-helix, whereupon cyclopropanation and branching activity competed with chain elongation. During the corresponding metamorphosis of CPPase to FPPase, cyclopropanation and branching activities were lost upon replacement of the first helix in the six-helix bundle. Mutations of active site residues in CPPase to the corresponding amino acids in FPPase enhanced chain-elongation activity, while similar mutations in the active site of FPPase failed to significantly promote formation of significant amounts of irregular monoterpenes. Our results indicate that CPPase, a promiscuous enzyme, is more plastic toward acquiring new activities, whereas FPPase is more resistant. Mutations of residues outside of the α terpene synthase fold are important for acquisition of FPPase activity for synthesis of CPP, LPP, and MPP.
- Lee, J. Scott,Pan, Jian-Jung,Ramamoorthy, Gurusankar,Poulter, C. Dale
-
p. 14556 - 14567
(2017/10/24)
-
- Enantiospecific Solvolytic Functionalization of Bromochlorides
-
Herein, we report that under mild solvolytic conditions, enantioenriched bromochlorides can be ionized, stereospecifically cyclized to an array of complex bromocyclic scaffolds, or intermolecularly trapped by exogenous nucleophiles. Mechanistic investigations support an ionic mechanism wherein the bromochloride serves as an enantioenriched bromonium surrogate. Several natural product-relevant motifs are accessed in enantioenriched form for the first time with high levels of stereocontrol, and this technology is applied to the scalable synthesis of a polycyclic brominated natural product. Arrays of nucleophiles including olefins, alkynes, heterocycles, and epoxides are competent traps in the bromonium-induced cyclizations, leading to the formation of enantioenriched mono-, bi-, and tricyclic products. This strategy is further amenable to intermolecular coupling between cinnamyl bromochlorides and a diverse set of commercially available nucleophiles. Collectively, this work demonstrates that enantioenriched bromonium chlorides are configurationally stable under solvolytic conditions in the presence of a variety of functional groups.
- Burckle, Alexander J.,Gál, Bálint,Seidl, Frederick J.,Vasilev, Vasil H.,Burns, Noah Z.
-
supporting information
p. 13562 - 13569
(2017/10/05)
-
- MANUFACTURING METHOD OF CARBOXYLIC ACID PRENYL AND PRENOL USING OXOVANADIUM COMPLEX
-
PROBLEM TO BE SOLVED: To provide an industrially and economically advantageous manufacturing method of carboxylic acid prenyl and prenol in a high yield under a mild condition. SOLUTION: In a manufacturing method, allyl alcohol represented by the formula (1) is reacted with carboxylic acid anhydride represented by the formula (2) in a presence of an oxovanadium complex prepared by reacting trialkoxy oxovanadium and a pyridinecarboxylic acid derivative, thereby obtaining allyl ester represented by the formula (3). Further, carboxylic acid prenyl is subjected to solvolysis, thereby obtaining prenol represented by the formula (4). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT
- -
-
Paragraph 0068
(2017/10/07)
-
- MANUFACTURING METHOD OF PRENYL CARBOXYLATES AND PRENOLS USING BIS(β-DIKETONATO)DIOXO MOLYBDENUM COMPLEX
-
PROBLEM TO BE SOLVED: To provide an environmental friendly, simple, safe and inexpensive manufacturing method of prenyl carboxylates and prenols which are useful as raw materials or synthetic intermediates of pharmaceuticals, agricultural chemicals, aromatics or the like. SOLUTION: There are provided a manufacturing method of prenyl carboxylates represented by the formula (3) by reacting allyl alcohols represents by the formula (1) with carboxylic acid anhydride represented by the formula (2) in a presence of bis(β-diketonato)dioxo molybdenum complex and further a manufacturing method of prenols represented by the formula (4) by solvolysis of prenyl carboxylates represented by the formula (3) with methanol or the like in a presence of a catalyst such as potassium carbonate. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT
- -
-
Paragraph 0048; 0049
(2017/08/04)
-
- PRODUCTION OF FARNESOL
-
The present invention relates to an improved way for the production of farnesol.
- -
-
Page/Page column 11
(2017/04/11)
-
- METHOD FOR PRODUCING PRENYL ESTERS AND PRENOLS
-
PROBLEM TO BE SOLVED: To provide an industrially and economically advantageous method for geometrically selectively producing prenol under a mild condition. SOLUTION: Provided is a method for producing prenyl ester (3) in which allyl alcohol (1) is reacted with vinyl ester (2) under the presence of an oxovanadium complex and a hydrolytic enzyme. Further provided is a method for producing prenol (4) by hydrolyzing prenyl ester (3). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
- -
-
Paragraph 0079
(2017/01/17)
-
- (2E, 6E) enriching [...] -
-
PROBLEM TO BE SOLVED: To provide a method for producing (2E, 6E)-farnesal useful as an intermediate for the production of a polyisoprenoid derivative useful as an anticancer agent.SOLUTION: The method for producing (2E, 6E)-farnesal includes heating (2Z, 6E)-farnesal in the presence of a piperidin-1-oxyl compound represented by formula (1) [wherein Ris a hydrogen atom; Ris a hydrogen atom, cyano, carboxy, isothiocyanato, maleimide, phosphate group, -OR' group or -NHR group (wherein R' is a hydrogen atom, 1-4C alkyl, acyl or 1-4C alkanesulfonyl; R is a hydrogen atom, acetyl or haloacetyl); or Rand Rtogether form an oxo group].
- -
-
Paragraph 0033
(2018/09/25)
-
- Synthesis method for trans, trans-farnesol
-
The invention discloses a synthesis method for trans, trans-farnesol. The synthesis technology includes the steps that geranyl acetate serves as an original raw material, and is oxidized through selenium dioxide and tert-butyl hydroperoxide, subjected to acid catalysis with dihydropyran to form acetal, saponified under the alkali condition and reacted with an isopentenyl Grignard reagent under existing of copper salt in sequence, four steps are carried out, and the trans, trans-farnesol is obtained, namely, (2E, 6E)-farnesol. According to the preparing method, the raw material is low and easy to obtain, operation is easy and operate, the reaction condition is mild, and industrial production is hoped to be achieved.
- -
-
-
- Organic Photocatalytic Cyclization of Polyenes: A Visible-Light-Mediated Radical Cascade Approach
-
A visible-light-mediated, organic photocatalytic stereoselective radical cascade cyclization of polyprenoids is described. The desired cascade cyclization products are achieved in good yields and high stereoselectivities with eosinY as photocatalyst in hexafluoro-2-propanol. The catalyst system is also suitable for 1,3-dicarbonyl compounds, which require only catalytic amounts of LiBr to promote the formation of the corresponding enols.
- Yang, Zhongbo,Li, Han,Zhang, Long,Zhang, Ming-Tian,Cheng, Jin-Pei,Luo, Sanzhong
-
supporting information
p. 14723 - 14727
(2015/10/19)
-
- Design, synthesis and anticancer activity evaluation of diazepinomicin derivatives
-
A series of diazepinomicin derivatives were synthesized and evaluated in vitro for their growth inhibitory activity against the human carcinoma cell lines. The results indicated the anticancer selectivity of this kind of compounds. Based on the results, preliminary structure-activity relationships were discussed.
- Yu, Yongguo,Wu, Jianbo,Lei, Fan,Chen, Lei,Wan, Weili,Hai, Li,Guan, Mei,Wu, Yong
-
p. 369 - 373
(2013/07/26)
-
- Method for Converting Farnesol to Nerolidol in the Presence of Alpha-Bisabolol
-
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.
- -
-
-
- Transpeptidase-mediated incorporation of d-amino acids into bacterial peptidoglycan
-
The β-lactams are the most important class of antibiotics in clinical use. Their lethal targets are the transpeptidase domains of penicillin binding proteins (PBPs), which catalyze the cross-linking of bacterial peptidoglycan (PG) during cell wall synthesis. The transpeptidation reaction occurs in two steps, the first being formation of a covalent enzyme intermediate and the second involving attack of an amine on this intermediate. Here we use defined PG substrates to dissect the individual steps catalyzed by a purified E. coli transpeptidase. We demonstrate that this transpeptidase accepts a set of structurally diverse d-amino acid substrates and incorporates them into PG fragments. These results provide new information on donor and acceptor requirements as well as a mechanistic basis for previous observations that noncanonical d-amino acids can be introduced into the bacterial cell wall.
- Lupoli, Tania J.,Tsukamoto, Hirokazu,Doud, Emma H.,Wang, Tsung-Shing Andrew,Walker, Suzanne,Kahne, Daniel
-
p. 10748 - 10751
(2011/09/13)
-
- Mn(0)-mediated chemoselective reduction of aldehydes. Application to the synthesis of α-deuterioalcohols
-
A mild, simple, safe, chemoselective reduction of different kinds of aldehydes to the corresponding alcohols mediated by the Mn dust/water system is described. In addition to this, the use of D2O leads to the synthesis of α-deuterated alcohols and constitutes an efficient, inexpensive alternative for the preparation of these compounds.
- Jimenez, Tania,Barea, Elisa,Oltra, J. Enrique,Cuerva, Juan M.,Justicia, Jose
-
experimental part
p. 7022 - 7025
(2010/11/18)
-
- Farnesyl diphosphate synthase: The art of compromise between substrate selectivity and stereoselectivity
-
Farnesyl diphosphate (FPP) synthase catalyzes the consecutive head-to-tail condensations of isopentenyl diphosphate (IPP, C5) with dimethylallyl diphosphate (DMAPP, C5) and geranyl diphosphate (GPP, C10) to give (E,E)-FPP (C15). The enzyme belongs to a genetically distinct family of chain elongation enzymes that install E-double bonds during each addition of a five-carbon isoprene unit. Analysis of the C10 and C15 products from incubations with avian FPP synthase reveals that small amounts of neryl diphosphate (Z-C10) and (Z,E)-FPP are formed along with the E-isomers during the C5 → C10 and C10 → C15 reactions. Similar results were obtained for FPP synthase from Escherichia coli, Artemisia tridentata (sage brush), Pyrococcus furiosus, and Methanobacter thermautotrophicus and for GPP and FPP synthesized in vivo by E. coli FPP synthase. When (R)-[2-2H]IPP was a substrate for chain elongation, no deuterium was found in the chain elongation products. In contrast, the deuterium in (S)-[2-2H]IPP was incorporated into all of the products. Thus, the pro-R hydrogen at C2 of IPP is lost when the E- and Z-double bond isomers are formed. The synthesis of Z-double bond isomers by FPP synthase during chain elongation is unexpected for a highly evolved enzyme and probably reflects a compromise between optimizing double bond stereoselectivity and the need to exclude DMAPP from the IPP binding site.
- Thulasiram, Hirekodathakallu V.,Poulter, C. Dale
-
p. 15819 - 15823
(2007/10/03)
-
- Synthesis of farnesol isomers via a modified wittig procedure
-
(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.
-
p. 4803 - 4806
(2007/10/03)
-
- A facile, catalytic, and environmentally benign method for selective deprotection of teri-butyldimethylsilyl ether mediated by phosphomolybdic acid supported on silica gel
-
An environmentally benign PMA supported on SiO2 is found to be an efficient catalyst for the chemoselective deprotection of TBDMS ethers under very mild conditions. Various labile functional groups such as isopropylidene acetal, OTBDPS, OTHP, Oallyl, OBn, alkene, alkyne, OAc, OBz, N-Boc, N-Cbz, N-Fmoc, mesylate, and azide are found to be stable under the reaction conditions. This "truly catalytic" heterogeneous reaction does not require aqueous workup, and the supported catalyst and the solvent can be readily recovered and recycled.
- Kishore Kumar,Baskaran, Sundarababu
-
p. 4520 - 4523
(2007/10/03)
-
- Toward higher polyprenols under 'prebiotic' conditions
-
Geraniol and isomers (C10) can be obtained by the condensation of C5 monoprenols at room temperature in the presence of montmorillonite K-10. It is also possible to obtain farnesol (C15) and isomers by condensation of geraniol with isopentenol. Despite the low yields achieved, these findings support the hypothesis that polyprenyl phosphates may have been formed in prebiotic conditions, and served as constituents of primitive membranes.
- Désaubry, Laurent,Nakatani, Yoichi,Ourisson, Guy
-
p. 6959 - 6961
(2007/10/03)
-
- Compounds having protected hydroxy groups
-
The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
- -
-
-
- Natural and unnatural terpenoid precursors of insect juvenile hormone
-
The biosynthesis of insect juvenile hormone (JH) is due, in part, to the precise head-to-tail coupling of allylic and homoallylic diphosphate substrates, as catalyzed by one or more prenyltransferases. To better understand this enzyme's role in JH production, homodimethylallyl diphosphate and both the natural and unnatural homologs of geranyl diphosphate have been prepared as potential substrates for insect prenyltransferase. These latter materials were constructed in a convergent manner by olefination of the corresponding trisnoraldehydes obtained from either terminal oxidative cleavage of geraniol or higher-order cuprate conjugate addition to acrolein. To aid in characterizing the nature of the terpenoid skeletons formed from our in vitro studies, homologous derivatives of farnesol were also prepared by anion coupling of the geranyl derivatives to either C5 or C6 allylic bromides. The preparation of these materials and the results of incubations with larval corpora allata homogenates of the lepidopteran Manduca sexta are described.
- Sen, Stephanie E.,Ewing, Gregory J.
-
p. 3529 - 3536
(2007/10/03)
-
- Synthesis of (2E,6E)-[10-3H]farnesol and (2E,6E)-[10-3H]farnesal for insect dehydrogenase studies
-
[10-3H]Farnesol ((2E,6E)-3,7,11-trimethyl-2,6,10-dodecatrien-1-ol) and [10-3H]farnesal ((2E,6E)-3,7,11-trimethyl-2,6,10- -dodecatrian-1-al) were synthesized by sequential reduction and oxidation of the corresponding tert-butyldiphenylsilyl protected 11,12,13-trisnoraldehyde, followed by Wittig homologation using isopropyltriphenylphosphorane. Direct reduction of the C-12 allylic bromide or allylic chloride proved to be an nonviable method, resulting in either multiple decomposition products or significant double bond transposition. Oxidation of the [10-3H]labelled trisnoralcohol with pyridinium chlorochromate resulted in essentially complete retention of the radiolabel as was established for the corresponding deuterated material. [3H]labelled farnesol and farnesal were obtained in 78% and 74% yields, respectively, from the trisnoraldehyde. These materials were used as radiotracers for examining the enzymatic activity of insect farnesol and farnesal dehydrogenase, key enzymes in the biosynthesis of juvenile hormone.
- Sen,Garvin
-
p. 1063 - 1069
(2007/10/02)
-
- Phosphorus-containing squalene synthetase inhibitors
-
Compounds which are inhibitors of cholesterol biosynthesis (by inhibiting de novo squalene biosynthesis), and thus are useful as hypocholesterolemic agents and antiatherosclerotic agents are provided which have the structure STR1 wherein m is 0, 1, 2 or 3; n is 0, 1, 2, 3 or 4; Y1 and Y2 are H or halogen; R2, R3 and R4 may be the same or different and are independently H, metal ion, C1 to C8 alkyl or C3 to C12 alkenyl; X is O, S, NH or NCH2 R15 wherein R15 is H or C1 to C5 alkyl; and R1 is R5 --Q1 --Q2 --Q3 -- wherein R5, Q1, Q2 and Q3 are as defined herein; and when m is o, X is other than S; and if m is o and X is 0, then n is 1, 2, 3 or 4; including all stereoisomers thereof.
- -
-
-
- Facile and Stereospecific Synthesis of (S)- and (R)-Isopentenyl Pyrophosphates
-
(S)- and (R)-Isopentenyl pyrophosphates, which are useful precursors for stereochemical studies on the biosynthesis of isoprenoids, were chemically synthesized in five steps via (S)- and (R)-3-methyl-2,3-epoxybutan-1-ols starting with 3,3-dimethylallyl alcohol, in 18 percent and 15 percent overall yields, respectively.
- Suga, Takayuki,Ohta, Shinji,Ohmoto, Tatsuya
-
p. 2845 - 2848
(2007/10/02)
-
- β,γ-dihydropolyprenyl alcohol derivatives and pharmaceutical composition containing a polyprenyl compound
-
A β,γ-dihydropolyprenyl alcohol derivative having the formula: STR1 wherein n is an integer of 5 to 7 and R is hydrogen, a lower alkyl group or an aliphatic or aromatic acyl group, is new and useful as a phylactic agent against human and animal infectious diseases. Other disclosed polyprenyl compounds are also useful as such agents.
- -
-
-
- CHEMICAL STUDIES OF BRITISH COLUMBIA NUDIBRANCHS
-
The chemical constituents of the skin extracts of several nudibranchs have been examined.Extracts of Archidoris montereyensis contain the diterpenoic acid glyceride 20, its two monoacetates 24 and 25, the drimane sesquiterpenoic acid glyceride 26, the monoacetate 28, the monocyclofarnesic acid glyceride 30 and the glyceryl ether 31.Glyceride 20 has also been isolated from extracts of Archidoris odhneri.The odiferous principle of Anisodoris nobilis extracts was shown to be the degraded sesquiterpenoid 33.Polycera tricolor extracts contain triophamine (19) as their major constituent. 14C labelled mevalonic acid is incorporated into the diterpenoic acid glyceride 20 and the sesquiterpenoic acid glyceride 26 by A. montereyensis, and into the farnesic acid glyceride 12 by A. odhneri.The drimenoic acid glyceride 26 and the glyceryl ether 31 show antifeedant activity against the tide pool sculpin Oligocottus maculosus.
- Gustafson, Kirk,Andersen, Raymond J.
-
p. 1101 - 1108
(2007/10/02)
-
- Synthesen von Carotinen mit ψ-Endgruppen und (Z)-Konfiguration an terminalen konjugierten Doppelbindungen
-
Five carotenes bearing (5Z)-ψ-end groups were synthesized and carefully characterized: (5Z)-lycopene (6), (5Z,5'Z)-lycopene (7), (5'Z)-neurosporene (8), (5'Z)-β,ψ-carotene (12), and (5'Z)-εψ-carotene (14).
- Zumbrunn, Albrecht,Uebelhart, Peter,Eugster, Conrad Hans
-
p. 1519 - 1539
(2007/10/02)
-
- OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XXI. EFFECTIVE STEREOSPECIFIC SYNTHESIS OF (E,E)-FARNESOL AND (E,E,E)-GERANYLGERANIOL FROM 1,5,9-TRIMETHYL-(E,E,E)-1,5,9-CYCLODODECATRIENE
-
A new method was developed for the stereospecific synthesis of (E,E)-farnesol and (E,E,E)-geranylgeraniol, based on the selective ozonolysis of 1,5,9-trimethyl-(E,E,E)-1,5,9-cyclododecatriene - a readily obtainable oligomer of isoprene.The subsequent transformations of the obtained 4-methyl-1,1-dimethoxy-8-oxo-4E-nonene and 4,8-dimethyl-1,1-dimethoxy-12-oxo-4E,8E-tridecadiene, including ethoxycarbonylolefination at the keto group and Z/E isomerization of the esters of the α,β-unsaturated carboxylic acids, lead to the desired compounds with total yields of 22 and 25percent respectively.
- Odinokov, V. N.,Kukovinets, O. S.,Sakharova, N. I.,Tolstikov, G. A.
-
p. 1702 - 1707
(2007/10/02)
-
- A Regiocontrolled Annulation Approach to Highly Substituted Aromatic Compounds
-
The thermal combination of cyclobutenone derivatives with heterosubstituted acetylenes provides a regiocontrolled route to highly substitutted aromatic compounds
- Danheiser, Rick L.,Gee, Stephen K.
-
p. 1672 - 1674
(2007/10/02)
-
- SYNTHESE A L'AIDE DE SULFONES-XXVI. SYNTHESE D'ALCOOLS ALLYLIQUES ET DE POLYPRENOLS PAR ATTACHEMENT D'UN SYNTHON PRENOL EN POSITION 4 E
-
The E-hydroxyalkylsulphone PhSO2CH2C(CH3)=CHCH2OH is regioselectively and stereoselectively substituted by Grignard reagents in the presence of copper(II) acetylacetonate, giving E allylic alcohols in high yield.A recurrent synthesis of polyprenols and an efficient preparation of the African Monarch pheromone are described.
- Julia, Marc,Verpeaux, Jean-Noel
-
p. 3289 - 3292
(2007/10/02)
-
- PHOTOCHEMICAL TRANSFORMATIONS-III; ORGANIC IODIDES (Part 3): GERANYL AND NERYL IODIDES AND 2(E),6(E)- AND 2(Z),6(E)-FARNESYL IODIDES
-
Solution photolysis of geranyl and neryl iodides, and 2(E),6(E)- and 2(Z),6(E)-farnesyl iodides has been carried out.Products arising from simple elimination as well as ?-participation are formed.Thus, both geranyl and neryl iodides furnished, besides some unidentified compounds, myrcene, cis-ocimene, limonene and terpinolene, though in different proportions.Likewise, the sesquiterpene analogues yielded different amounts of trans-β-farnesene, β-bisabolene, trans-α-bisabolene and ar-curcumene.Results have been discussed in terms of ionic intermediates.
- Saplay, K. M.,Damodaran, N. P.,Dev, Sukh
-
p. 2999 - 3004
(2007/10/02)
-
- SELECTIVE ALLYLIC REARRANGEMENT WITH TUNGSTEN CATALYST
-
Selective thermal rearrangement of allylic alcohols proceeds in the presence of various O=W(OR)4.Ligand catalysts wich are more stable than O=W(OR)4 catalyst and are several times more active than O=V(OR)3 catalyst.
- Hosogai, Takeo,Fujita, Yoshiji,Ninagawa, Yoichi,Nishida, Takashi
-
p. 357 - 360
(2007/10/02)
-
- Stereoselective Synthesis of Solanesol and all-trans-Decaprenol
-
Allylic p-tolyl sulphonates (5), (14), and (16) couple with allylic bromide (7) and geranyl bromide to produce regio- and stereo-chemically pure 1,5-diene systems.The coupling of all-trans-ω-bromogeranyl acetate (7) with geranyl p-tolyl sulphone (5) and higher isoprenologues (21), (24), and (27), followed by reductive elimination of p-tolylsulphonyl group, furnishes a stereoselective synthesis of all-trans-polyprenols (3), (23), (26), and decaprenol (1b).Solanesol (1a) was synthesised using trans-4-chloroprenyl acetate (29) instead of (7).
- Sato, Kikumasa,Inoue, Seiichi,Onishi, Akira,Uchida, Nobuhiko,Minowa, Nobuto
-
p. 761 - 769
(2007/10/02)
-
- Sur la stereochimie de la cyclisation du nerolidol an α-bisabolol
-
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
-
p. 387 - 392
(2007/10/02)
-
- Structure and Biosynthesis of Cleomeprenols from the Leaves of Cleome spinosa
-
Cleomeprenols isolated from Cleome spinosa L. (Capparidaceae) have been identified as nonaprenol (1), decaprenol (2), and undecaprenol (3), which are composed of an ω-terminal isoprene, three internal E-isoprene, and the remaining Z-isoprene residues, respectively.Feeding experiments using stereospecifically double-labelled radioactive mevalonate showed that all the cleomeprenols are composed of four biogenetically E- and the remaining biogenetically Z-isoprene residues.Occurence of the succesive cis-condensation of isoprene residues with (2E,6E,10E)-geranylgeranyl pyrophosphate was demonstrated by comparing the incorporation of a homologue of all-E-prenyl pyrophosphates with that of the corresponding 2Z-isomer.
- Suga, Takayuki,Shishibori, Tsuyoshi
-
p. 2098 - 2104
(2007/10/02)
-
- Inclusion complex compound, process for its production, and method for its use
-
An inclusion complex compound comprising (a) meta-cyclophane and (b) a trans-terpenoid of the formula STR1 wherein n is an integer of 1 to 9; A1 and A2 each represent (1) a hydrogen atom, (2) a halogen atom, (3) an inorganic group containing an oxygen, nitrogen or sulfur atom, (4) an organic group containing 1 to 5 carbon atoms, or (5) an organic group containing an oxygen, nitrogen or sulfur atom and 1 to 5 carbon atoms; and C* is the carbon atom of a carbonyl or methylene group, Included by the meta-cyclophane. This inclusion complex compound can be prepared by contacting the meta-cyclophane with a mixture containing the trans-terpenoid. A trans-terpenoid can be separated from a mixture containing it by utilizing an inclusion complex compound of it with meta-cyclophane.
- -
-
-
