- Photocatalytic Transfer Hydrogenolysis of Allylic Alcohols on Pd/TiO2: A Shortcut to (S)-(+)-Lavandulol
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We report herein a regio- and stereoselective photocatalytic hydrogenolysis of allylic alcohols to form unsaturated hydrocarbons employing a palladium(II)-loaded titanium oxide; the reaction proceeds at room temperature under light irradiation without stoichiometric generation of salt wastes. Olefin and saturated alcohol moieties tolerated the reaction conditions. Hydrogen atoms were selectively incorporated into less sterically congested carbons of the allylic functionalities. This protocol allowed a short-step synthesis of (S)-(+)-lavandulol from (R)-(?)-carvone by avoiding otherwise necessary protection/deprotection steps.
- Takada, Yuki,Caner, Joaquim,Kaliyamoorthy, Selvam,Naka, Hiroshi,Saito, Susumu
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supporting information
p. 18025 - 18032
(2017/12/08)
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- Structure-Function Studies of Artemisia tridentata Farnesyl Diphosphate Synthase and Chrysanthemyl Diphosphate Synthase by Site-Directed Mutagenesis and Morphogenesis
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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
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p. 14556 - 14567
(2017/10/24)
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- Fungal mediated kinetic resolution of racemic acetates to (R)-alcohols using Fusarium proliferatum
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Fungal mediated kinetic resolution of seven acyclic/aromatic acetates was achieved using Fusarium proliferatum to furnish (R)-alcohols in high enantiomeric excess (>95%). The kinetic resolution was established as one-pot two-step de-esterification/oxidation biocatalytic process. Further, the preparative scale synthesis of (R)-(+)-1-phenylethanol was accomplished through de-esterification/oxidation of (±)-1-phenylethyl acetate using the whole cell of F. proliferatum NCIM 1105.
- Jadhav, Dipesh D.,Patil, Harshal S.,Chaya, Patil S.,Thulasiram, Hirekodathakallu V.
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p. 4563 - 4567
(2016/09/23)
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- METHOD OF MONITORING AND/OR CONTROLLING THYSANOPTERA
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The present invention provides a method of monitoring or controlling Thysanoptera (hereafter thrips) using a behaviour-modifying compound of Formula (1), wherein Formula (1) is: where R1 is a C2-C8 straight or branched alkenyl group and the * denotes a stereocentre. Suitably, the method involves providing the behaviour-modifying compound at a pre- determined location. Typically the behaviour-modifying compound is released or broadcast within an area infested (or potentially infested) by thrips. This can be achieved by using a lure or other release device comprising a compound of Formula (1), for example to attract the thrips to a trap.
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Page/Page column 35-36
(2014/05/24)
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- A Synthesis of (-)-(R)- and (+)-(S)-Lavandulol, (+)-Lavandulyl 2-methylbutanoate, and (+)-lavandulyl senecioate through orthoester johnson-claisen rearrangement
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An efficient synthesis of (-)-(R)- and (+)-(S)-lavandulol, (+)-lavandulyl 2-methylbutanoate and (+)-lavandulyl senecioate is presented in this paper. The synthetic strategy features a chiral-pool approach to an allyl alcohol intermediate, and an orthoester Johnson-Claisen rearrangement as the key step. An efficient synthesis of (-)-(R)- and (+)-(S)-lavandulol, (+)-lavandulyl 2-methylbutanoate and (+)-lavandulyl senecioate is presented. The synthetic strategy features a chiral-pool approach to an allyl alcohol intermediate, and an orthoester Johnson-Claisen rearrangement as the key step. Copyright
- Fernandes, Rodney A.,Chowdhury, Asim K.
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p. 5165 - 5170
(2013/11/06)
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- The biosynthetic origin of irregular monoterpenes in lavandula: Isolation and biochemical characterization of a novel cis-prenyl diphosphate synthase gene, lavandulyl diphosphate synthase
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Lavender essential oils are constituted predominantly of regular monoterpenes, for example linalool, 1,8-cineole, and camphor. However, they also contain irregular monoterpenes including lavandulol and lavandulyl acetate. Although the majority of genes responsible for the production of regular monoterpenes in lavenders are now known, enzymes (including lavandulyl diphosphate synthase (LPPS)) catalyzing the biosynthesis of irregular monoterpenes in these plants have not been described. Here, we report the isolation and functional characterization of a novel cis-prenyl diphosphate synthase cDNA, termed Lavandula x intermedia lavandulyl diphosphate synthase (LiLPPS), through a homology-based cloning strategy. The LiLPPS ORF, encoding for a 305-amino acid long protein, was expressed in Escherichia coli, and the recombinant protein was purified by nickel-nitrilotriacetic acid affinity chromatography. The approximately 34.5-kDa bacterially produced protein specifically catalyzed the head-to-middle condensation of two dimethylallyl diphosphate units to LPP in vitro with apparent Km and k cat values of 208 ± 12 μM and 0.1 s-1, respectively. LiLPPS is a homodimeric enzyme with a sigmoidal saturation curve and Hill coefficient of 2.7, suggesting a positive co-operative interaction among its catalytic sites. LiLPPS could be used to modulate the production of lavandulol and its derivatives in plants through metabolic engineering.
- Demissie, Zerihun A.,Erland, Lauren A.E.,Rheault, Mark R.,Mahmoud, Soheil S.
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p. 6333 - 6341
(2013/05/09)
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- Chemomicrobial synthesis of (R)- and (S)-lavandulol
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(R)- and (S)-Lavandulol are important compounds in the cosmetics industry and in pheromone research. We have developed syntheses of (R)- and (S)-lavandulol from (S)- and (R)-limonene, respectively, by microbial Baeyer-Villiger oxidation of the intermediate unsaturated hydroxy ketone. It has been found that the same strain of Acremonium roseum can be successfully used in the key step of the synthesis of both enantiomers of lavandulol.
- Gliszczynska, Anna,Bonikowski, Radoslaw,Kula, Jozef,Wawrzenczyk, Czeslaw,Ciolak, Kornelia
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p. 4461 - 4463
(2011/09/19)
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- A common mechanism for branching, cyclopropanation, and cyclobutanation reactions in the isoprenoid biosynthetic pathway
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Four reactions - chain elongation, cyclopropanation, branching, and cyclobutanation - are used in nature to join isoprenoid units for construction of the carbon skeletons for over 55 000 naturally occurring isoprenoid compounds. Those molecules produced by chain elongation have head-to-tail (regular) carbon skeletons, while those from cyclopropanation, branching, or cyclobutanation have non-head-to-tail (irregular) skeletons. Although wild type enzymes have not been identified for the branching and cyclobutanation reactions, chimeric proteins constructed from farnesyl diphosphate synthase (chain elongation) and chrysanthemyl diphosphate synthase (cyclopropanation) catalyze all four of the known isoprenoid coupling reactions to give a mixture of geranyl diphosphate (chain elongation), chrysanthemyl diphosphate (cyclopropanation), lavandulyl diphosphate (branching), and maconelliyl and planococcyl diphosphate (cyclobutanation). Replacement of the hydrogen atoms at C1 or C2 or hydrogen atoms in the methyl groups of dimethylallyl diphosphate by deuterium alters the distribution of the cyclopropanation, branching, and cyclobutanation products through primary and secondary kinetic isotope effects on the partitioning steps of common carbocationic intermediates. These experiments establish the sequence in which the intermediates are formed and indicate that enzyme-mediated control of the carbocationic rearrangement and elimination steps determines the distribution of products.
- Thulasiram, Hirekodathakallu V.,Erickson, Hans K.,Poulter, C. Dale
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p. 1966 - 1971
(2008/09/18)
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- A convenient resolution of racemic lavandulol through lipase-catalyzed acylation with succinic anhydride: Simple preparation of enantiomerically pure (R)-lavandulol
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(R)- and (S)-lavandulol and their esters are important compounds in perfumery and have recently become significant in pheromone research. (R)-Lavandulol and its esters, as well as the esters of (S)-lavandulol have been identified as sex and aggregation pheromones in two mealybugs, in thrips and in weevils. We report a convenient resolution of racemic lavandulol through lipase-catalyzed acylation with succinic anhydride. This method does not require tedious chromatographic separation and is particularly suitable for the preparation of enantiomerically pure (R)-lavandulol with 98% ee in one resolution cycle. The (S)-lavandulol with 90% ee can be obtained by a second resolution cycle.
- Zada, Anat,Dunkelblum, Ezra
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p. 230 - 233
(2007/10/03)
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- Enzymatic transesterification of racemic lavandulol: Preparation of the two enantiomeric alcohols and of the two enantiomers of lavandulyl senecioate
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(R) and (S)-lavandulol are important compounds in the cosmetics industry and in pheromone research. The senecioyl ester of (S)-lavandulyl has recently been identified as the sex pheromone of the vine mealybug, a significant pest in vineyards. We herein report the preparation of the two enantiomers of lavandulol and lavandulyl senecioate, starting from racemic lavandulol. The preparation is based on a two-cycle enzymatic transesterification of racemic lavandulol with vinyl acetate using Porcine pancreas lipase. High enantioselectivity was achieved while the preparation yielded (R)-lavandulol with 96.7% ee and (S)-lavandulol with 92.6% ee.
- Zada, Anat,Harel, Miriam
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p. 2339 - 2343
(2007/10/03)
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- Asymmetric α-alkylation of α,β-unsaturated esters. Application to the synthesis of (R)-lavandulol, (R)-sesquilavandulol and related trifluoromethyl compounds
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Diastereoselective α-alkylation/deconjugation of esters of diacetone D-glucose has been performed and applied to the syntheses of (R)-lavandulol, (R)-sesquilavandulol with de up to 74%. The same reaction performed with trifluoromethyl derivatives was also
- Faure,Piva
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p. 1414 - 1416
(2007/10/03)
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- Enantio- and diastereoselective protonation of photodienols: Total synthesis of (R)-(-)-lavandulol
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The total synthesis of (R)-(-)-lavandulol 1 has been achieved by asymmetric protonation of photodienols obtained from the irradiation of prochiral α,β-unsaturated esters. The photodeconjugation of ethyl 5-methyl-2-(1'-methylethylidene)-4-hexenoate (3a), carried out in the presence of catalytic amounts of a β-amino alcohol prepared from (±)-camphor, gives the β,γ-unsaturated isomer 2a in good yields but with moderate enantioselectivities (40% ee). In contrast, irradiation of the corresponding ester 3b, bearing the 1,2:5,6-di-O-isopropylidene-D-glucose group as a chiral alkoxy moiety, affords the deconjugated product 2b in high de (> 95%). Simple reduction of the ester function with LiAlH4 gives (R)-(-)-lavandulol (1) without loss of optical purity.
- Piva
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p. 7879 - 7883
(2007/10/03)
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- C45- and C50-Carotenoids, 1st Communication. Synthesis of (R)- and (S)-Lavandulol
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Starting with methyl (3R)-3-hydroxybutanoate ((R)-7) and ethyl (3S)-3-hydroxybutanoate ((S)-11), respectively, (R)- and (S)-lavandulol ((R)-1 and (S)-1) were synthesized with high optical purity.The synthesized key intermediates (R)-6 and (S)-6 are suitable compounds for the synthesis of optically active acyclic C45- and C50-carotenoids.
- Kramer, Andreas,Pfander, Hanspeter
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p. 293 - 301
(2007/10/02)
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