- Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β-Unsaturated Ketones
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Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.
- Beltran, Frédéric,Bergamaschi, Enrico,Funes-Ardoiz, Ignacio,Teskey, Christopher J.
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supporting information
p. 21176 - 21182
(2020/09/17)
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- Total Synthesis of (?)-Rotundone and (?)-epi-Rotundone from Monoterpene Precursors
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The first total synthesis of (?)-rotundone has been accomplished from (+)-(R)-limonene and therefore for the first time from an unrelated monoterpene instead of modifying structurally closely related sesquiterpene precursors such as α-guaiene. Challenges such as intermediates with stereocenters prone to epimerization by enolization were overcome by designing a β-methyl-keto route starting from (+)-(R)-limonene which finally gave (?)-rotundone by Nazarov cyclization of a precursor 13a. Diastereomer (?)-epi-rotundone was separated from (?)-rotundone chromatographically. An alternative route from rac-citronellal provided a diastereomer mixture of racemic Nazarov precursor 13 through a TRIP-catalyzed intramolecular aldolization, thus indicating that the Nazarov cyclization precursor 13a is in principle accessible from (?)-(S)-citronellal. The 11-step synthesis from (+)-(R)-limonene with ca. 1 % overall yield confirmed the absolute configuration of (?)-rotundone and provided samples of good olfactory quality.
- Rüthi, Fabian,Schr?der, Fridtjof
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- Synthesis and Biochemical Evaluation of Nicotinamide Derivatives as NADH Analogue Coenzymes in Ene Reductase
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Nicotinamide and pyridine-containing conjugates have attracted a lot of attention in research as they have found use in a wide range of applications including as redox flow batteries and calcium channel blockers, in biocatalysis, and in metabolism. The interesting redox character of the compounds’ pyridine/dihydropyridine system allows them to possess very similar characteristics to the natural chiral redox agents NAD+/NADH, even mimicking their functions. There has been considerable interest in designing and synthesizing NAD+/NADH mimetics with similar redox properties. In this research, three nicotinamide conjugates were designed, synthesized, and characterized. Molecular structures obtained through X-ray crystallography were obtained for two of the conjugates, thereby providing more detail on the bonding and structure of the compounds. The compounds were then further evaluated for biochemical properties, and it was found that one of the conjugates possessed similar functions and characteristics to the natural NADH. This compound was evaluated in the active enzyme, enoate reductase; like NADH, it was shown to help reduce the C=C double bond of three substrates and even outperformed the natural coenzyme. Kinetic data are reported.
- Falcone, Natashya,She, Zhe,Syed, Jebreil,Lough, Alan,Kraatz, Heinz-Bernhard
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p. 838 - 845
(2019/02/07)
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- C3 and C6 Modification-Specific OYE Biotransformations of Synthetic Carvones and Sequential BVMO Chemoenzymatic Synthesis of Chiral Caprolactones
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The scope for biocatalytic modification of non-native carvone derivatives for speciality intermediates has hitherto been limited. Additionally, caprolactones are important feedstocks with diverse applications in the polymer industry and new non-native terpenone-derived biocatalytic caprolactone syntheses are thus of potential value for industrial biocatalytic materials applications. Biocatalytic reduction of synthetic analogues of R-(?)-carvone with additional substituents at C3 or C6, or both C3 and C6, using three types of OYEs (OYE2, PETNR and OYE3) shows significant impact of both regio-substitution and the substrate diastereomer. Bioreduction of (?)-carvone derivatives substituted with a Me and/or OH group at C6 is highly dependent on the diastereomer of the substrate. Derivatives bearing C6 substituents larger than methyl moieties are not substrates. Computer docking studies of PETNR with both (6S)-Me and (6R)-Me substituted (?)-carvone provides a model consistent with the outcomes of bioconversion. The products of bioreduction were efficiently biotransformed by the Baeyer–Villiger monooxygenase (BVase) CHMO_Phi1 to afford novel trisubstituted lactones with complete regioselectivity to provide a new biocatalytic entry to these chiral caprolactones. This provides both new non-native polymerization feedstock chemicals, but also with enhanced efficiency and selectivity over native (+)-dihydrocarvone Baeyer–Villigerase expansion. Optimum enzymatic reactions were scaled up to 60–100 mg, demonstrating the utility for preparative biocatalytic synthesis of both new synthetic scaffold-modified dihydrocarvones and efficient biocatalytic entry to new chiral caprolactones, which are potential single-isomer chiral polymer feedstocks.
- Issa, Issa S.,Toogood, Helen S.,Johannissen, Linus O.,Raftery, James,Scrutton, Nigel S.,Gardiner, John M.
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supporting information
p. 2983 - 2988
(2019/01/24)
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- Heteropoly acid catalysis for the isomerization of biomass-derived limonene oxide and kinetic separation of the trans-isomer in green solvents
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Terpenes are an abundant class of natural products, which is important for flavor and fragrance industry. Many acid catalyzed reactions used for upgrading terpenes still involve mineral acids as homogeneous catalysts and/or toxic solvents. Heteropoly acids represent a well-established eco-friendly alternative to conventional acid catalysts. As these reactions are usually performed in the liquid phase, solvents play a critical role for the process sustainability. In the present work, we developed a catalytic route to valuable fragrance ingredients, dihydrocarvone and carvenone, from limonene oxide by its isomerization using silica-supported tungstophosphoric acid as a heterogeneous catalyst and dialkylcarbonates as green solvents. The reaction pathway can be switched between dihydrocarvone and carvenone (obtained in 90% yield each) simply by changing the reaction temperature. In addition, we developed an efficient method for kinetic separation of trans-limonene oxide from commercial cis/trans-limonene oxide mixture and stereoselective synthesis of trans-dihydrocarvone.
- Cotta, Rafaela F.,Martins, Rafael A.,Pereira, Matheus M.,da Silva Rocha, Kelly A.,Kozhevnikova, Elena F.,Kozhevnikov, Ivan V.,Gusevskaya, Elena V.
-
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- Hydrogenation of Carbonyl Derivatives Catalysed by Manganese Complexes Bearing Bidentate Pyridinyl-Phosphine Ligands
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Manganese(I) catalysts incorporating readily available bidentate 2-aminopyridinyl-phosphine ligands achieve a high efficiency in the hydrogenation of carbonyl compounds, significantly better than parent ones based on more elaborated and expensive tridentate 2,6-(diaminopyridinyl)-diphosphine ligands. The reaction proceeds with low catalyst loading (0.5 mol%) under mild conditions (50 °C) with yields up to 96%. (Figure presented.).
- Wei, Duo,Bruneau-Voisine, Antoine,Chauvin, Téo,Dorcet, Vincent,Roisnel, Thierry,Valyaev, Dmitry A.,Lugan, No?l,Sortais, Jean-Baptiste
-
supporting information
p. 676 - 681
(2017/12/26)
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- Enantio- A nd regioselective: Ene-reductions using F420H2-dependent enzymes
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In the past decade it has become clear that many microbes harbor enzymes that employ an unusual flavin cofactor, the F420 deazaflavin cofactor. Herein we show that F420-dependent reductases (FDRs) can successfully perform enantio-, regio- A nd chemoselective ene-reductions. For the first time, we have demonstrated that F420H2-driven reductases can be used as biocatalysts for the reduction of α,β-unsaturated ketones and aldehydes with good conversions (>99%) and excellent regioselectivities and enantiomeric excesses (>99% ee). Noteworthily, FDRs typically display an opposite enantioselectivity when compared to the well established FMN-dependent Old Yellow Enzymes (OYEs).
- Mathew, Sam,Trajkovic, Milos,Kumar, Hemant,Nguyen, Quoc-Thai,Fraaije, Marco W.
-
supporting information
p. 11208 - 11211
(2018/10/15)
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- Investigating: Saccharomyces cerevisiae alkene reductase OYE 3 by substrate profiling, X-ray crystallography and computational methods
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Saccharomyces cerevisiae OYE 3 shares 80% sequence identity with the well-studied Saccharomyces pastorianus OYE 1; however, wild-type OYE 3 shows different stereoselectivities toward some alkene substrates. Site-saturation mutagenesis of Trp 116 in OYE 3 followed by substrate profiling showed that the mutations had relatively little effect, opposite to that observed previously for OYE 1. The X-ray crystal structures of unliganded and phenol-bound OYE 3 were solved to 1.8 and 1.9 ? resolution, respectively. Both structures were nearly identical to that of OYE 1, with only a single amino acid difference in the active site region (Ser 296 versus Phe 296, part of loop 6). Despite their essentially identical static X-ray structures, molecular dynamics (MD) simulations revealed that loop 6 conformations differed significantly in solution between OYE 3 and OYE 1. In OYE 3, loop 6 remained nearly as open as observed in the crystal structure; by contrast, loop 6 closed over the active site of OYE 1 by ca. 4 ?. Loop closure likely generates a greater number of active site protein contacts for substrate bound to OYE 1 as compared to OYE 3. These differences provide an explanation for the differing stereoselectivities of OYE 3 and OYE 1, despite their nearly identical X-ray crystal structures.
- Powell, Robert W.,Buteler, M. Pilar,Lenka, Sunidhi,Crotti, Michele,Santangelo, Sara,Burg, Matthew J.,Bruner, Steven,Brenna, Elisabetta,Roitberg, Adrian E.,Stewart, Jon D.
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p. 5003 - 5016
(2018/10/17)
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- Novel concurrent redox cascades of (R)- and (S)-carvones enables access to carvo-lactones with distinct regio- and enantioselectivity
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Within this study, we investigated a one-pot enzymatic redox cascade composed of different enoate reductases (5 EREDs from diverse bacterial origins) and various Baeyer-Villiger monooxygenases (4 BVMOs) with complementary regioselectivity that enabled access to six out of eight carvo-lactone stereoisomers starting from readily available natural carvones. Applicability of this two-step cascade was demonstrated by preparative scale experiments yielding up to 76% of the desired chiral carvolactone.
- Iqbal, Naseem,Stewart, Jon D.,Macheroux, Peter,Rudroff, Florian,Mihovilovic, Marko D.
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p. 7389 - 7394
(2018/11/23)
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- Stereodivergent Synthesis of Carveol and Dihydrocarveol through Ketoreductases/Ene-Reductases Catalyzed Asymmetric Reduction
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Chiral carveol and dihydrocarveol are important additives in the flavor industry and building blocks in the synthesis of natural products. Despite the remarkable progress in asymmetric catalysis, convenient access to all possible stereoisomers of carveol and dihydrocarveol remains a challenge. Here, we present the stereodivergent synthesis of carveol and dihydrocarveol through ketoreductases/ene-reductases catalyzed asymmetric reduction. By directly asymmetric reduction of (R)- and (S)-carvone using ketoreductases, which have Prelog or anti-Prelog stereopreference, all four possible stereoisomers of carveol with medium to high diastereomeric excesses (up to >99 %) were first observed. Then four stereoisomers of dihydrocarvone were prepared through ene-reductases catalyzed diastereoselective synthesis. Asymmetric reduction of obtained dihydrocarvone isomers by ketoreductases further provide access to all eight stereoisomeric dihydrocarveol with up to 95 % de values. In addition, the absolute configurations of dihydrocarveol stereoisomers were determined by using modified Mosher's method.
- Guo, Jiyang,Zhang, Rui,Ouyang, Jingping,Zhang, Feiting,Qin, Fengyu,Liu, Guigao,Zhang, Wenhe,Li, Hengyu,Ji, Xiaohong,Jia, Xian,Qin, Bin,You, Song
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p. 5496 - 5504
(2018/11/30)
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- Transfer hydrogenation of ketones catalyzed by iridium-bulky phosphine complexes
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The complexes [Ir(COD)(PR3)2]PF6 (R = PPh3 (1); R = PBn3 = tribenzylphosphine (2)), [Ir(COD)(PBn3)(PAn3)]PF6 (3) (PAn3 = Tri-orthoanisyl-phosphine) and cis-(P,P)-[IrH(COD)(PBn3){η2-P,C-(C6H4CH2)PBn2}]PF6 (4) are active in the transfer hydrogenation of ketones. However, complex (3) gives the best results in conversion toward the alcohol. Interestingly, commercial isopropanol was used as hydrogen source, without any drying treatment. In situ generated isopropoxide was used as base. An efficient conversion of a variety of ketones, aromatic or aliphatic, cyclic or linear, including molecules with conjugated or isolated C[dbnd]C moieties was achieved, thus reporting 12 examples of hydrogenated substrates. Ketones of higher steric hindrance could not be converted under the studied conditions. The experimental evidence indicates that the steric and electronic properties of the substrates are determinant in the observed conversions and performance of the system. For α,β-unsaturated ketones, preference toward the reduction of the C[dbnd]C bond was observed. However, the system shows chemoselectivity toward the carbonyl group in molecules which also bear an isolated C[dbnd]C moiety. With the results obtained, a pseudo first-order dependence of the reaction rate on the concentration of ketone was determined. Also, stoichiometric as well as in situ tests were performed to shed light into the reaction pathways possibly involved in the catalytic TH of ketones described herein (precursor 3, base and isopropyl alcohol as hydrogen source).
- Landaeta, Vanessa R.,Rosa, Abel D. Salazar-La,Rodríguez-Lugo, Rafael E.
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p. 303 - 311
(2017/09/06)
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- Kinetics of the Aqueous Phase Reactions of Atmospherically Relevant Monoterpene Epoxides
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Laboratory and field measurements have demonstrated that an isoprene-derived epoxide intermediate (IEPOX) is the origin of a wide range of chemical species found in ambient secondary organic aerosol (SOA). In order to explore the potential relevance of a similar mechanism for the formation of monoterpene-derived SOA, nuclear magnetic resonance techniques were used to study kinetics and reaction products of the aqueous-phase reactions of several monoterpene epoxides: β-pinene oxide, limonene oxide, and limonene dioxide. The present results, combined with a previous study of α-pinene oxide, indicate that all of these epoxides will react more quickly than IEPOX with aqueous atmospheric particles, even under low-acidity conditions. As for α-pinene oxide, the observed products can be mainly rationalized with a hydrolysis mechanism, and no long-lived organosulfate or nitrate species nor species that retain the β-pinene bicyclic carbon backbone are observed. As bicyclic ring-retaining organosulfate and nitrate species have been previously observed in monoterpene-derived SOA, it appears that monoterpene-derived epoxides may not be as versatile as IEPOX in producing a range of SOA species, and other mechanisms are needed to rationalize organosulfate and nitrate formation.
- Cortés, DIego A.,Elrod, Matthew J.
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p. 9297 - 9305
(2017/12/18)
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- Ene Reductase Enzymes for the Aromatisation of Tetralones and Cyclohexenones to Naphthols and Phenols
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Ene reductases (EREDs) have great potential as oxidation biocatalysts, as demonstrated by their efficient conversion of a number of tetralones to the corresponding naphthols. Of 96 enzymes tested, 57 were able to produce 2-naphthol in this way. Further tests with substituted tetralones revealed typically high conversions up to >99%. The reactions were performed under mild conditions in aqueous buffer with only co-solvent, biocatalyst and oxidation substrate required for conversion. Production of a methoxy-substituted naphthol was also successfully performed on a gram scale, with 91% yield. This methodology provides a new avenue to produce substituted naphthols as valuable building blocks, with the possibility to extend the approach to the production of phenols also being demonstrated.
- Kelly, Paul P.,Lipscomb, David,Quinn, Derek J.,Lemon, Ken,Caswell, Jill,Spratt, Jenny,Kosjek, Birgit,Truppo, Matthew,Moody, Thomas S.
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supporting information
p. 731 - 736
(2016/03/09)
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- Selective one-pot carvone oxime hydrogenation over titania supported gold catalyst as a novel approach for dihydrocarvone synthesis
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It was shown for the first time that dihydrocarvone can be selectively produced by gold-catalyzed one-pot transformation of carvone oxime. This reaction was carried out at 100 °C under hydrogen pressure of 9 bar over 1.9 wt.% Au/TiO2 catalyst using methanol as a solvent. Dihydrocarvone synthesis was shown to occur via carvone formation with the subsequent hydrogenation of its conjugated C=C double bond. Application of Au/TiO2 catalyst for both deoximation and selective hydrogenation of olefinic C=C functional group is reported for the first time. The combination of these steps provides optimization of the synthetic method for dihydrocarvone production from carvone oxime which is a key intermediate in carvone synthesis from limonene. Despite a lower reaction rate than in the case of carvone, a significant increase in the stereoselectivity towards trans-dihydrocarvone was observed in the case of carvone oxime hydrogenation. The ratio between trans- and cis-dihydrocarvone was close to 4.0 compared to 1.8 achieved in the case of carvone hydrogenation.
- Demidova, Yu. S.,Suslov,Simakova,Volcho,Salakhutdinov,Simakova,Murzin, D. Yu.
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p. 142 - 148
(2016/06/13)
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- Cell-free protein engineering of Old Yellow Enzyme 1 from Saccharomyces pastorianus
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In protein engineering, cell-free transcription/translation of linear mutagenic DNA templates can tremendously accelerate and simplify the screening of enzyme variants. Using the RApid Parallel Protein EvaluatoR (RAPPER) protocol, we have evaluated the impact of amino acid substitutions and loop truncations on substrate specificity and stereoselectivity of Old Yellow Enzyme 1 from Saccharomyces pastorianus. Our study demonstrates the benefit of systematically assessing amino acid variations including substrate profiling to explore sequence-function space.
- Quertinmont, Leann T.,Lutz, Stefan
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p. 7282 - 7287
(2016/10/29)
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- New biobased tetrabutylphosphonium ionic liquids: Synthesis, characterization and use as a solvent or co-solvent for mild and greener Pd-catalyzed hydrogenation processes
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Phosphonium-based Ionic Liquids (PhosILs) with natural organic derived anions (l-lactate, l-tartrate, malonate, succinate, l-malate, pyruvate, d-glucuronate, d-galacturonate, ferulate, p-coumarate) were easily prepared by acid-base method from tetrabutylphosphonium hydroxide and an excess of the corresponding acid with good yields. Their characterization was realized through classical NMR, IR and elemental analysis techniques; their viscosity and ATG parameters were also determined. These ionic liquids showed good performance and recyclability in the selective Pd-catalyzed hydrogenation of alkenes, polyenes like linoleic acid and enantioselective hydrogenation of unsaturated ketones such as isophorone at room temperature under atmospheric H2 pressure. Furthermore, NMR studies leading to computational calculations were performed to establish easily the composition of the resulting mixture obtained through the hydrogenation of linoleic acid.
- Hayouni, Safa,Robert, Anthony,Ferlin, Nadège,Amri, Hassen,Bouquillon, Sandrine
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p. 113583 - 113595
(2016/12/16)
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- Method for synthesizing dihydrocarvone by use of epoxy limonene
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The invention discloses a method for synthesizing dihydrocarvone by use of epoxy limonene. The method comprises the following steps: step 1, mixing epoxy limonene with a main catalyst A or an aided catalyst B, and heating to trigger a ring-opening rearrangement reaction, so as to generate dihydrocarvone; step 2, after the reaction is finished, adding white oil into the reaction liquid, and carrying out rectification to obtain a finished product of dihydrocarvone, wherein the main catalyst A is divalent-zinc lewis acid, and the aided catalyst B comprises one or two of organic alkali, ester or acyl ketone compounds. The method has the following advantages: the raw materials are easy to synthesize, cheap, and easy to obtain; no solvent is needed in the reaction process, so that the synthesis technology is environmentally friendly; post-processing purification can be achieved only through rectification, therefore the post-processing purification technology is simple; the selected catalyst can be recycled, and the method is suitable for industrialized production.
- -
-
Paragraph 0018
(2016/11/09)
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- Structural insights into stereospecific reduction of α, β-unsaturated carbonyl substrates by old yellow enzyme from Gluconobacter oxydans
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We report the crystal structure of old yellow enzyme (OYE) family protein Gox0502 (a.a 1-315) in free form at 3.3 ?. Detailed structural analysis revealed the key residues involved in stereospecific determination of Gox0502, such as Trp66 and Trp100. Structure-based computational analysis suggested the bulky side chains of these tryptophan residues may play important roles in product stereoselectivity. The introduction of Ile or Phe or Tyr mutation significantly reduced the product diastereoselectivity. We hypothesized that less bulky side chains at these critical residues could create additional free space to accommodate intermediates with different conformations. Notably, the introduction of Phe mutation at residue Trp100 increased catalytic activity compared to wild-type Gox0502 toward a set of substrates tested, which suggests that a less bulky Phe side chain at residue W100F may facilitate product release. Therefore, Gox0502 structure could provide useful information to generate desirable OYEs suitable for biotechnological applications in industry.
- Yin, Bo,Deng, Jian,Lim, Lirong,Yuan, Y. Adam,Wei, Dongzhi
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p. 410 - 421
(2015/08/11)
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- Selective carvone hydrogenation to dihydrocarvone over titania supported gold catalyst
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Selective hydrogenation of natural carvone to industrially valuable dihydrocarvone was carried out at 100°C under hydrogen pressure over a 1.9wt.% Au/TiO2 catalyst. The gold catalyst has demonstrated high activity as well as stereo- and chemoselectivity in conjugated C=C double bond hydrogenation with predominant formation of trans-dihydrocarvone. The catalytic activity and trans-to cis-isomers ratio were shown to strongly depend on the solvent. In a range of C1 - C3 alcohol solvents both catalytic activity and trans-to cis-dihydrocarvone ratio increased following the order: 2-propanol a nearly complete carvone conversion (90%) after 13h in the case of methanol, with the trans-to cis-dihydrocarvone ratio being about 1.8. Based on the transition state theory a quantitative description of trans-to cis-dihydrocarvone ratio variations in different solvents was made.
- Demidova,Suslov,Simakova,Simakova,Volcho,Salakhutdinov,Murzin
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p. 189 - 194
(2015/03/14)
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- Microwave assisted bi-functional activation of β-bromo-tert-alcohols
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Microwave-assisted dehydration-oxidation of β-bromo-tert-alcohols to afford 2,3-unsaturated ketones in good yield is reported. The reaction of substrates with DMSO in 1:1 ratio (w/v) is promoted by ZnS in a solvent-free condition. A concurrent bi-functional activation of trans-vicinal bromo- and hydroxyl groups with ZnS is elucidated. This is a new observation under microwave and applies to β-bromo-tert-alcohols derived from 1,4-disubstitued-1-cyclohexenes. It is very useful in the synthesis of 2,3-unsaturated ketones derived from monoterpenes which are valuable flavour compounds. [Figure not available: see fulltext.]
- Kannan, Nandini,Rangaswamy, Manjunatha Javagal,Kemapaiah, Bettadaiah Bheemanakere
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p. 1405 - 1410
(2015/11/09)
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- Production of flavours and fragrances via bioreduction of (4R)-(-)-carvone and (1R)-(-)-myrtenal by non-conventional yeast whole-cells
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As part of a program aiming at the selection of yeast strains which might be of interest as sources of natural flavours and fragrances, the bioreduction of (4R)-(-)-carvone and (1R)-(-)-myrtenal by whole-cells of non-conventional yeasts (NCYs) belonging to the genera Candida, Cryptococcus, Debaryomyces, Hanseniaspora, Kazachstania, Kluyveromyces, Lindnera, Nakaseomyces, Vanderwaltozyma and Wickerhamomyces was studied. Volatiles produced were sampled by means of headspace solid-phase microextraction (SPME) and the compounds were analysed and identified by gas chromatography-mass spectroscopy (GC-MS). Yields (expressed as % of biotransformation) varied in dependence of the strain. The reduction of both (4R)-(-)-carvone and (1R)-(-)-myrtenal were catalyzed by some ene-reductases (ERs) and/or carbonyl reductases (CRs), which determined the formation of (1R,4R)-dihydrocarvone and (1R)-myrtenol respectively, as main flavouring products. The potential of NCYs as novel whole-cell biocatalysts for selective biotransformation of electron-poor alkenes for producing flavours and fragrances of industrial interest is discussed.
- Goretti, Marta,Turchetti, Benedetta,Cramarossa, Maria Rita,Forti, Luca,Buzzini, Pietro
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p. 5736 - 5748
(2013/07/19)
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- Heteropoly acid catalysts for the synthesis of fragrance compounds from biorenewables: Isomerization of limonene oxide
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The liquid-phase isomerization of limonene oxide was studied in the presence of heteropoly acid catalysts in aprotic solvents in homogeneous and heterogeneous systems. Among the catalysts were bulk and silica-supported tungstophosphoric acid H3PW12O40 and its acidic Cs salt Cs0.5H0.5PW12O40 (CsPW). The reaction gave dihydrocarvone, a valuable fragrance intermediate, as the main product with turnover numbers of up to 8000. The nature of the solvent had a strong effect on reaction rate and selectivity. CsPW (0.1 mol%) was found to be a highly efficient and truly heterogeneous catalyst for this reaction, providing 82% yield of dihydrocarvone in 1,4-dioxane as a solvent under ambient conditions. This simple catalytic method represents economically attractive route to industrially important compounds starting from bio-renewable substrates easily available from essential oils. The Royal Society of Chemistry 2013.
- Costa, Vinicius V.,Da Silva Rocha, Kelly A.,Kozhevnikov, Ivan V.,Kozhevnikova, Elena F.,Gusevskaya, Elena V.
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p. 244 - 250
(2013/04/10)
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- Asymmetric reduction of (4R)-(-)-carvone catalyzed by Baker's yeast in aqueous mono- and biphasic systems
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(1R,4R)-dihydrocarvone (2), an important renewable building block, was prepared with good conversions and excellent diastereoisomeric excess through the reduction of the α,β-unsatured carbon-carbon double bond of (4R)-(-)-carvone (1) mediated by Baker's yeast (BY) in aqueous mono- and biphasic systems. Some parameters that may alter this bioreduction reaction, such as the concentrations of yeast and substrate, temperature, and pH, were evaluated. The effect of the addition of different additives on the course of 1 biotransformation was also investigated. The results showed that the conversion and diastereoisomeric excesses were strongly dependent on these variables. The optimum reaction conditions were 100 g L-1 of BY, 16.6 mM of substrate, and pH 7.5 at 26 °C in the presence of DMSO, trehalose, or sucrose as additives. Under the optimum conditions, the (1R,4R)-dihydrocarvone was recovered with diastereoisomeric excesses of 92-99% and with conversions of 70-74%.
- Silva, Vanessa Dutra,Stambuk, Boris Ugarte,Nascimento, Maria Da Graa
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experimental part
p. 98 - 104
(2012/06/30)
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- A base-promoted deprotection of 1,3-dioxolanes to ketones
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An effective deprotection methodology of dioxolanes was developed, affording moderate to excellent yield via a LTMP-promoted reaction in THF, which displays admirable chemoselectivity in the presence of dimethylketal, 1,3-dioxane, 1,3-dithiane, or other acid-sensitive protective groups.
- Yuan, Changchun,Yang, Li,Yue, Guizhou,Yu, Tianzi,Zhong, Weiming,Liu, Bo
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supporting information
p. 6972 - 6976
(2013/01/15)
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- Use of immobilized transition metal complexes as recyclable catalysts for oxidation reactions with hydrogen peroxide as oxidant
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A tetradentate Schiff base (teta), obtained from triethylenetetramine and salicylaldehyde, has been covalently bonded to divinylbenzene cross-linked chloromethylated polystyrene. This chelating ligand, abbreviated as PS-teta (PS = polymeric support), reacts with metal chlorides (Cu2+, Co 2+, and Ni2+) in methanol to give polymerbound transition metal complexes, PS-Cu(II)teta/(Cat-1), PS-Ni(II)teta/(Cat-2), and PS-Co(II)teta/(Cat-3), formation of which has been established by various physiochemical methods and spectroscopic techniques. The catalytic potential of these materials has been tested for the oxidation of various alkenes, alkanes, alcohols, and thioethers in the presence of 30% H2O2 as an oxidant. At the same time, these catalysts are very stable and could be reused in oxidation reactions for more than five times without noticeable loss of their catalytic activity. Springer Science+Business Media B.V. 2011.
- Islam, Sk Manirul,Mobarok, Manir,Mondal, Paramita,Roy, Anupam Singha,Salam, Noor,Hossain, Dildar,Mondal, Sanchita
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experimental part
p. 97 - 107
(2012/09/22)
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- A Site-Saturated Mutagenesis Study of Pentaerythritol Tetranitrate Reductase Reveals that Residues 181 and 184 Influence Ligand Binding, Stereochemistry and Reactivity
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We have conducted a site-specific saturation mutagenesis study of H181 and H184 of flavoprotein pentaerythritol tetranitrate reductase (PETN reductase) to probe the role of these residues in substrate binding and catalysis with a variety of α,β-unsaturated alkenes. Single mutations at these residues were sufficient to dramatically increase the enantiopurity of products formed by reduction of 2-phenyl-1-nitropropene. In addition, many mutants exhibited a switch in reactivity to predominantly catalyse nitro reduction, as opposed to C=C reduction. These mutants showed an enhancement in a minor side reaction and formed 2-phenylpropanal oxime from 2-phenyl-1-nitropropene. The multiple binding conformations of hydroxy substituted nitro-olefins in PETN reductase were examined by using both structural and catalytic techniques. These compounds were found to bind in both active and inhibitory complexes; this highlights the plasticity of the active site and the ability of the H181/H184 couple to coordinate with multiple functional groups. These properties demonstrate the potential to use PETN reductase as a scaffold in the development of industrially useful biocatalysts. Divergent evolution: A site-saturation study of PETN reductase was performed at conserved substrate binding residues H181 and H184. These residues were shown to dramatically alter the ratio of alkene versus nitro-group reduction in favour of oxime by-product formation, as summarised in the picture.
- Toogood, Helen S.,Fryszkowska, Anna,Hulley, Martyn,Sakuma, Michiyo,Mansell, David,Stephens, Gill M.,Gardiner, John M.,Scrutton, Nigel S.
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scheme or table
p. 738 - 749
(2012/02/01)
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- (R)-(-)-carvone and (1R, 4R)-trans-(+)-dihydrocarvone from Poiretia latifolia vogel
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The essential oils of Poiretia latifolia Vogel, native and cultivated leaves (Samples A and B, respectively) and native flowers (sample C), were obtained by hydrodistillation and analyzed by GC, GC/MS and chiral phase gas chromatography (CPGC). Twenty-four compounds were identified, representing 99.25, 99.26 and 99.23percent of the oils, respectively. The major constituents of the oils were the monoterpenes (S)-(-)-limonene (16.05, 27.60, 15.60percent, respectively), (1R, 4R)-trans-(+)-dihydrocarvone (18.05, 0.66 and 77.80percent, respectively) and (R)-(-)-carvone (61.05, 64.20 and 4.50percent, respectively). The essential oils were evaluated against some strains of Gram (+) and Gram (-) bacteria, and yeast, but displayed only modest antimicrobial activity.
- Porto, Carla,Stu?ker, Caroline Z.,Mallmann, Anderson S.,Simionatto, Euclesio,Flach, Adriana,Do Canto-Dorow, Tais,Da Silva, Ubiratan F.,Dalcol, Ionara I.,Morel, Ademir F.
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scheme or table
p. 782 - 786
(2010/11/17)
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- pH-dependent catalytic activity and chemoselectivity in transfer hydrogenation catalyzed by iridium complex with 4,4′-dihydroxy-2,2′- bipyridine
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Transfer hydrogenation catalyzed by an iridium catalyst with 4,4′dihydroxy-2,2′-bipyridine (DHBP) in an aqueous formate solution exhibits highly pH-dependent catalytic activity and chemoselectivity. The substantial change in the activity is due to the electronic effect based on the acid-base equilibrium of the phenolic hydroxyl group of DHBP. Under basic conditions, high turnover frequency values of the DHBP complex, which can be more than 1000 times the value of the unsubstituted analogue, are obtained (up to 81000 h-1 at 80°C). In addition, the DHBP catalyst exhibits pH-dependent chemoselectivity for α,β-unsaturated carbonyl compounds. Selective reduction of the C=C bond of enone with high activity are observed under basic conditions. The ketone moieties can be reduced with satisfactory activity under acidic conditions. In particular, pH-selective chemoselectivity of the C=O versus C=C bond reduction was observed in the transfer hydrogenation of cinnamaldehyde.
- Himeda, Yuichiro,Onozawa-Komatsuzaki, Nobuko,Miyazawa, Satoru,Sugihara, Hideki,Hirose, Takuji,Kasuga, Kazuyuki
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scheme or table
p. 11076 - 11081
(2009/11/30)
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- Acid-catalyzed reactions of sarcophytoxide, a marine cembranoid: An apparently enantio-directive reaction, unusual products and stereochemical reconsideration of epoxide-ketone rearrangement
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Perchloric acid treatment of sarcophytoxide, a marine cembranoid possessing an epoxide, brought about epoxide ketone rearrangement affording ketones. When the reaction time was long (22 h), a minor ketone that was antipodal to the ketone obtained in a short-time (l0min) reaction was formed. These puzzling findings, considering that the starting epoxide had three asymmetric carbons, were interpreted by surveying the structures of other ketonic products. The stereochemistry of a major ketone, which had been wrongly assigned, was corrected by extensive analyses of NMR spectra. The correct stereochemistry indicated that the epoxide-ketone rearrangement took a course via a cationic intermediate.
- Nii, Keiji,Tagami, Keiko,Rijima, Masaru,Munakata, Tatsuo,Ooi, Takashi,Kusumi, Takenori
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experimental part
p. 562 - 573
(2009/04/10)
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- Microbial Baeyer-Villiger oxidation of terpenones by recombinant whole-cell biocatalysts - Formation of enantiocomplementary regioisomeric lactones
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Recombinant whole-cell expression systems for Baeyer-Villiger monooxygenases of various bacterial origin were utilized in the regiodivergent biooxidation of cyclic terpenones enabling access to enantio- and regioisomeric lactones on preparative scale. This journal is The Royal Society of Chemistry.
- Ernuchova, Petra,Mihovilovic, Marko D.
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p. 1715 - 1719
(2008/02/10)
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- Daucus carota and baker's yeast mediated bio-reduction of prochiral ketones
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Stereoselective reduction of prochiral ketones to the corresponding alcohols using biocatalysts has attracted much attention, from the viewpoint of green chemistry. Asymmetric reduction of indanone, tetralone and hydroxyl trimonoterpene ketones to the corresponding enantiomerically pure (S)-alcohols, using Daucus carota plant homogenate and fermented baker's yeast cells, is described. The present study illustrates the broad substrate selectivity of the dehydrogenase enzymes present in the D. carota in the synthesis of a wide range of chiral secondary alcohols of biological importance.
- Yadav, Jhillu S.,Reddy, Garudammagari S.K.K.,Sabitha, Gowravaram,Krishna, Avvaru D.,Prasad, Attaluri R.,Hafeez-U-R-Rahaman,Vishwaswar Rao, Katta,Bhaskar Rao, Adari
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p. 717 - 723
(2008/02/02)
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- A facile and chemoselective conjugate reduction using polymethylhydrosiloxane (PMHS) and catalytic B(C6F5) 3
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A highly chemoselective conjugate reduction of electron-deficient Michael acceptors, including Α, β-unsaturated ketones, carboxylic esters, nitriles and nitro compounds with PMHS in the presence of catalytic B(C 6F5)3 was investigated. When attempts were made to improve the yields by increasing the amount of catalyst, the result was a complex mixture of saturated and unsaturated compounds, with partial reduction of the ketone moiety to the methylene functionality. PMHS along with a catalytic amount of B(C6F5)3 was found to be a unique reagent system for the conjugate reduction of Michael acceptors.
- Chandrasekhar, Srivari,Chandrashekar, Gudise,Reddy, Marepally Srinivasa,Srihari, Pabbaraja
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p. 1650 - 1652
(2008/02/03)
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- Synthetic scope of alcohol transfer dehydrogenation catalyzed by Cu/Al 2O3: A new metallic catalyst with unusual selectivity
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A method for the anaerobic oxidation of a wide series of alcohols including cyclohexanols and steroidal alcohols, has been set up. It relies on a transfer dehydrogenation reaction from the substrate alcohol to styrene catalyzed by a heterogeneous, reusable copper catalyst under very mild liquid phase experimental conditions (90°C, N2) and shows unusual selectivity. Thus, the method is selective for the oxidation of secondary and allylic alcohols even in the presence of unprotected primary and benzylic alcohols. Electronic effects and the choice of the hydrogen acceptor account for the selectivity observed.
- Zaccheria, Federica,Ravasio, Nicoletta,Psaro, Rinaldo,Fusi, Achille
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p. 6426 - 6431
(2008/09/20)
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- A metal-free catalytic reduction of α,β-unsaturated carbonyl compounds with phenyldimethylsilane
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Selective reduction of α,β-unsaturated carbonyl compounds to the corresponding saturated ones by phenyldimethyl silane was promoted by a catalytic amount of I2O5 at ambient temperature in CH 2CI2.
- Mu, Ruizhu,Liu, Zhengang,Liu, Zhongquan,Yang, Li,Wu, Longmin,Liu, Zhong-Li
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p. 469 - 470
(2007/10/03)
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- Radical hydrometalation of functional ethylenic compounds: Radical autoinhibition changes the regioselectivity
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Hydrometalation of carbon-carbon double bonds by group 14 hydrides is inhibited by carbonyl compounds-mainly by α,β-unsaturated carbonyl groups-as efficiently as by classical radical trapping compounds, such as galvinoxyl and hydroquinone. This phenomenon
- El Kadib, Abdelkrim,Feddouli, Amal,Riviere, Pierre,Delpech, Fabien,Riviere-Baudet, Monique,Castel, Annie,Ahra, Mohamed,Hasnaoui, Aissa,Burgos, Francisco,Manriquez, Juan M.,Chavez, Ivone
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p. 446 - 454
(2008/10/09)
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- Anaerobic oxidation of non-activated secondary alcohols over Cu/Al 2O3
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A liquid phase, transfer dehydrogenation reaction promoted by an 8% Cu/Al2O3 catalyst allows complete conversion of secondary alcohols into ketones under very mild conditions and in short times without any additives.
- Zaccheria, Federica,Ravasio, Nicoletta,Psaro, Rinaldo,Fusi, Achille
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p. 253 - 255
(2007/10/03)
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- Asymmetric reduction of enones with Synechococcus sp. PCC 7942
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Synechococcus sp. PCC 7942, a cyanobacterium, reduced both the endocyclic C-C double bond of s-trans enones and the exocyclic C-C double bond of s-cis enones with high enantioselectivity to afford the corresponding (S)-ketones under illumination.
- Shimoda, Kei,Kubota, Naoji,Hamada, Hiroki,Kaji, Misato,Hirata, Toshifumi
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p. 1677 - 1679
(2007/10/03)
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- Asymmetric transformation of enones with Synechococcus sp. PCC 7942
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Asymmetric transformation of enones was investigated with cultured cells of Synechococcus sp. PCC 7942 (a cyanobacterium). The cells reduced both the endocyclic C-C double bond of s-trans enones and the exocyclic C-C double bond of s-cis enones with high enantioselectivity to afford optically active α-substituted (S)-ketones under illumination. In addition, the reduction of the double bond of these enones was accompanied by the formation of saturated alcohols. The cells preferentially reduced simple aliphatic ketones rather than cyclic ones to the corresponding (S)-alcohols with excellent enantioselectivity.
- Shimoda, Kei,Kubota, Naoji,Hamada, Hiroki,Yamane, Shin-Ya,Hirata, Toshifumi
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p. 2269 - 2272
(2007/10/03)
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- SnCl2-SiO2: A selective reagent for efficient regeneration of carbonyls from nitrogeneous derivatives
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Semicarbazones, Phenyl hydrazones, 2,4-DNP and Oxime derivatives are converted into corresponding carbonyl compounds, mostly in quantitative yield by stannous chloridesilica gel. This has general application to various nitrogeneous derivatives.
- Das, Nalin B.,Nanda, Bhagabat,Nayak, Amalendu
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p. 3647 - 3651
(2007/10/03)
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- Tetramethyldiamidophosphoric acid chloride mediated epoxide-diene conversion and steroidal aromatization
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The reaction of tetramethyldiamidophosphoric acid chloride with epoxides in the presence of a trace amount of water furnished 1,3-dienes in good yield. The conversion works with open chain and cyclic epoxides. A C-C bond cleavage reaction occurs if the epoxide contains a quaternary carbon. Application of this method to epoxy sterols afforded ring A aromatic steroids in good yield. The aromatization works via dienol-benzene rearrangements and is independent of the C-3 stereochemistry.
- Demir, Ayhan S
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p. 227 - 233
(2007/10/03)
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- A 38 kDa allylic alcohol dehydrogenase from the cultured cells of Nicotiana tabacum
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An NADP+-dependent alcohol dehydrogenase (allyl-ADH) was isolated from the cultured cells of Nicotiana tabacum. The allyl-ADH was found to be efficient for the dehydrogenation of secondary allylic alcohols rather than saturated secondary alcohols and it was specific for the S-stereoisomer of the alcohols. The enzyme catalyzed the reversible reaction whereby the carbonyl group of enones is reduced to the corresponding allylic alcohol or vice versa. Two possible primary structures of the allyl-ADH were deduced by the sequence analyses of full-length cDNAs (ally-ADH1 and ally-ADH2), which were cloned by the PCR method. These analyses indicated that the allyl-ADHs are composed of 343 amino acids-having the molecular weights 38 083 and 37 994, respectively, and they showed approximately 70% homology to the NADP+-dependent oxidoreductases belonging to a plant ζ-crystallin family. (C) 2000 Elsevier Science Ltd.
- Hirata, Toshifumi,Tamura, Yoshitaka,Yokobatake, Naoyuki,Shimoda, Kei,Ashida, Yoshiyuki
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p. 297 - 303
(2007/10/03)
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- PCC oxidation of organoboranes obtained using acetoxyborohydride
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The selective hydroboration with acetoxyborohydride of dienes and functionalized olefins followed by PCC oxidation afford the corresponding carbonyl derivatives.
- Dhillon, Ranjit S.,Kaur, Avinder Pal,Kaur, Gurpreet
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p. 453 - 454
(2007/10/03)
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- Conjugate reduction of α,β-unsaturated ketones with hydrosilane mediated by copper(I) salt
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Reduction of several α,β-unsaturated ketones with dimethylphenylsilane and 10-100 mol% of CuF(PPh3)3 · 2EtOH or CuCl/PPh3/Bu4NF proceeds in a 1,4-selective manner to give the corresponding saturated ketones in up to >99% yield.
- Mori, Atsunori,Fujita, Akinori,Kajiro, Hiroshi,Nishihara, Yasushi,Hiyama, Tamejiro
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p. 4573 - 4582
(2007/10/03)
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- Binreduction of (R)-carvone and regioselective baeyer-villiger oxidations: Application to the asymmetric synthesis of cryptophycin fragment A
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Cryptophycin fragment A (1) was prepared in high enantiomeric purity in 10 steps from (R)-carvone. A stereoselective bioreduction of (R)-carvone to neodihydrocarveol and a regioselective Baeyer-Villiger oxidation of cyclohexanone 8 with pertrifluoroacetic acid were employed in this synthesis.
- Varie, David L.,Brennan, John,Briggs, Barbara,Cronin, Jason S.,Hay, David A.,Rieck III, John A.,Zmijewski, Milton J.
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p. 8405 - 8408
(2007/10/03)
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- Copper(I) salt mediated 1,4-reduction of α,β-unsaturated ketones using hydrosilanes
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Reduction of α,β-unsaturated ketones with HSiPhMe2 in the presence of CuF(PPh3)3·2EtOH proceeds in a 1,4-selective manner to give the corresponding saturated ketones in excellent yields.
- Mori, Atsunori,Fujita, Akinori,Nishihara, Yasushi,Hiyama, Tamejiro
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p. 2159 - 2160
(2007/10/03)
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- Generation of a reducing reagent from Copper(I) salt and hydrosilane. New practical method for conjugate reduction
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Hydride transfer from a hydrosilane to a copper(I) salt is reported. The silicon group of hydrosilanes was smoothly replaced by copper(I) chloride in DMI to give the corresponding metal hydride complex of copper(I). This transformation was applied to conjugate reduction of α,β-unsaturated compounds with a hydrosilane mediated by copper(I) chloride.
- Ito, Hajime,Ishizuka, Tomoko,Arimoto, Kikuo,Miura, Katsukiyo,Hosomi, Akira
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p. 8887 - 8890
(2007/10/03)
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- Selective oxidation of primary alcohols with quinolinium chlorochromate
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Selective oxidation of primary alcohol in the presence of a secondary alcohol with quinolinium chlorochromate (QCC) has been achieved with a mild, stable and very efficient reagent. Its mechanistic and comparative study with isoquinolinium chlorochromate (IQCC) has also been reported.
- Singh, Jasvinder,Kad, G. L.,Vig, Shikha,Sharma, Munisha,Chhabra, B. R.
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p. 272 - 274
(2007/10/03)
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- Metalloporphyrin as an efficient catalyst in the regioselective isomerization of epoxides to carbonyl compounds
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Regioselective ring-opening isomerization of epoxides to carbonyl compounds can effectively be catalyzed by iron (III) tetraphenylporphyrin, Fe(tpp)ClO4.
- Takanami, Toshikatsu,Hirabe, Rina,Ueno, Masayoshi,Hino, Fumio,Suda, Kohji
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p. 1031 - 1032
(2007/10/03)
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- Selective 1,4-Reduction of Conjugated Aldehydes and Ketones in the Presence of Unconjugated Aldehydes and Ketones with Sodium Dithionite
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Chemoselective 1,4-reduction of α,β-unsaturated aldehydes or ketones has been achieved with sodium dithionite in H2O/dioxane at 50 deg C in the presence of unsaturated (nonconjugated) and saturated aldehydes or ketones.
- Dhillon, Ranjit S.,Singh, Rupinder P.,Kaur, Daljit
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p. 1107 - 1108
(2007/10/02)
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