• Title/Summary/Keyword: Cyclic ketone reduction

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Selective Reduction of Organic Compounds with Non-Free Hydride Reducing Agents

  • Cha, Jin Soon
    • Journal of Integrative Natural Science
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    • v.1 no.3
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    • pp.192-194
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    • 2008
  • A series of non-free hydride reducing systems containing boron or aluminum atom, which possess no metal-hydride bond but an available hydrogen at a branched ${\beta}$-position, has been applied to the selective reduction (chemo--, regio-, and stereoselective reduction) of organic compounds. The systems, comprised of diisopinocampheylborane and diisobutylalane derivatives, exhibited almost perfect selectivities in the reduction of aldehydes and ketones. The characteristics features of this systems leading to a perfect transformation have been depicted in this report, especially in the 1) Reduction of ${\alpha}$,${\beta}$-Unsaturated Carbonyl Compounds to Allylic Alcohols via 1,2-Reduction, 2) Chemoselective Reduction between Structurally Different Carbonyl Compounds, and 3) Stereoselective Reduction of Cyclic Ketones.

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Selective Reduction of Carbonyl Compounds with Al-Alkoxydiisobutylalanes

  • 차진순;권오운;김종미;전중현;이영수;이형수;조성동
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.236-242
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    • 1998
  • Reaction of carbonyl compounds with Al-alkoxydiisobutylalane (DIBAOR, R=H, Et, i-Pr, t-Bu) has been investigated in detail so as to establish their usefulness as selective reducing agents in organic synthesis. The reagents appear to be extremely mild and can reduce only aldehydes and ketones effectively under mild conditions. All the other common organic functional groups are not affected by these reagents. The reagents can also reduce α,β-unsaturated aldehydes and ketones to the corresponding allylic alcohols without any detectable 1,4-reduction. Furthermore, the reagents show a highly chemoselective discrimination between aldehyde and ketone, between aldehydes, and between ketones. Even more remarkable is the stereoselective reduction of cyclic ketones to the thermodynamically more stable alcohol epimers.

A Study on the Adsorption Effect of Korean zeolite "Clinoptilolite" as Cigarette Cavity Filter Additive. (한국산 Zeolite의 필터첨가제로서의 흡착효과에 관하여)

  • Yang, Gwang-Gyu;Song, Chi-Hyeon;Kim, Chan-Ho
    • Journal of the Korean Society of Tobacco Science
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    • v.2 no.1
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    • pp.8-16
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    • 1980
  • The cavity of triple filter was filled with the mixture of clinoptilolite and charcoal(1:1, V/V). The particle size of clinoptilolite was 30$\pm$5 A.S.T.M mesh. The reduction effects of the important gaseous components by this mixture were obtained as follows: 1) In comparison with the normal cellulose acetate niter, the contents of nicotine and T.P.M. were reduced about 35% and 22% respectively. 2) Many aliphatic and cyclic compounds were also substantially reduced in an average of 60%. 3) In contrast with the charcoal, the removal efficiency of clinoptilolite was revealed as higher (15-20%) in case of aliphatic compounds than the one (10-15%) of cyclic compounds. The above results showed us that the removal function of gaseous components was quite complementary each other (charcoal and clinoptilolite).

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Characteristics of Non-biodegradable Substances in Landfill Leachate (매립장 침출수의 생물학적 난분해성물질 특성 규명)

  • Lim, Bong-Su;Park, Hye-Sook;Kim, Heung Rag
    • Journal of Korean Society on Water Environment
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    • v.21 no.5
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    • pp.484-489
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    • 2005
  • In order to determine the removal rate of non-biodegradable substances and the change of their structural properties, this study was carried out by an ozone-treatment experiment on leachate collected from the landfill area of D City in Chung chung nam-do and examined the change of the chemical properties of non-biodegradable substances. The main elements of non-biodegradable substances in landfill leachate were benzene, toluene, trichloroethane, trichloroethylene, xylene, etc. and the concentration of toluene was 15.7 mg/L on the average, benzene 7.2 mg/L, trichloroethane 1.1 mg/L, trichloroethylene 0.75 mg/L and xylene 0.5 mg/L. When leachate was treated with ozone for 10 min, 30 min and 60 min, UV absorbance was reduced with the increase of reaction time, and the reduction rate was 38.6% at 60 min. TOC was removed by 13.2% at 60 min. The low reduction rate of TOC may be because TOC reacts indirectly with OH radical produced from reaction with ozone while UV absorbance usually relies on direct reaction between organic matters and ozone molecules. Color was removed by up to 97%, which suggests that ozonation is highly effective in removing coloring elements in leachate. Sixteen kinds of non-biodegradable compounds were found in the leachate and most of them had the characteristic of aromatic hydrocarbon. Among them dibutyl phthalate was identical with a substance included in the list of US EPA, which is classified as a mutagen that may cause the mutation of genes and disorders in chromosomes. In addition, 2,5-Cyclohexadiene-1,4-dione, 1,2-Benzenedicarboxylic acid and butyl octyl ester were found to be similar to substances listed by USEPA. According to the result of analyzing structural changes before and after ozonation using GC-MS, cyclic compounds and aromatic compounds were observed in the original water and aliphatic compounds were newly observed after ozonation. In addition, through ozonation, humic substances of high molecular weight were oxidized and decomposed and produced low-molecular compounds such as aldehyde, ketone and carboxyl acid and highly biodegradable aliphatic carbon, which suggests the bio-degradability of non-biodegradable substances.

Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 2016.05a
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    • pp.19-20
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    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

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