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Pellynols M?O, cytotoxic polyacetylenic alcohols from a Niphates sp. marine sponge
Three new polyacetylenic alcohols, pellynols M?O (1–3), along with two known ones, melyne A (4) and melyne B (5), were isolated from a Niphates sp. marine sponge collected off the South China Sea. The structures of new compounds were determined based on a combination of 1D and 2D NMR analysis, ESI-MSn fragmentation, and chemical (ozonolysis) method. Their absolute configurations were assigned by modified Mosher's method. All the isolates showed potent cytotoxic activity against PC9 and HepG2 human cancer cell lines with IC50 values of 2.9–7.6 μM.
Wang, Jie,Liu, Li-Yun,Liu, Lei,Zhan, Kai-Xuan,Jiao, Wei-Hua,Lin, Hou-Wen
p. 3701 - 3706
(2018)
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Liglaurates A–E, cytotoxic bis(lauric acid-12yl)lignanoates from the rhizomes of Drynaria roosii Nakaike
Five undescribed bis(lauric acid-12-yl)lignanoates, liglaurates A–E, along with the known methyl and glyceryl 12-caffeoyloxylaurates were isolated from the rhizomes of Drynaria roosii Nakaike. Their structures including absolute configurations were determined by HRESIMS, NMR techniques, and ECD calculation. Liglaurates A–D were isolated as the racemates, among which (±)-liglaurate A and (±)-liglaurate B were synthesized by a metal-mediated oxidative coupling reaction and further resolved as the enantiomerically pure compounds. Liglaurates (+)-A, (?)-A, (+)-B, (?)-B, (±)-C and (±)-D exhibited remarkable cytotoxic activities against HeLa cell line, with the IC50 values of 0.11 ± 0.02, 0.24 ± 0.01, 0.02 ± 0.00, 0.13 ± 0.02, 0.34 ± 0.07 and 0.17 ± 0.01 μM, respectively.
He, Wenwen,Wang, Dongyang,Wang, Liping,Wu, Dan,Wufuer, Halidan,Xu, Yanchao,Zhu, Weiming
(2022/03/09)

Novel insights into oxidation of fatty acids and fatty alcohols by cytochrome P450 monooxygenase CYP4B1
CYP4B1 is an enigmatic mammalian cytochrome P450 monooxygenase acting at the interface between xenobiotic and endobiotic metabolism. A prominent CYP4B1 substrate is the furan pro-toxin 4-ipomeanol (IPO). Our recent investigation on metabolism of IPO related compounds that maintain the furan functionality of IPO while replacing its alcohol group with alkyl chains of varying structure and length revealed that, in addition to cytotoxic reactive metabolite formation (resulting from furan activation) non-cytotoxic ω-hydroxylation at the alkyl chain can also occur. We hypothesized that substrate reorientations may happen in the active site of CYP4B1. These findings prompted us to re-investigate oxidation of unsaturated fatty acids and fatty alcohols with C9–C16 carbon chain length by CYP4B1. Strikingly, we found that besides the previously reported ω- and ω-1-hydroxylations, CYP4B1 is also capable of α-, β-, γ-, and δ-fatty acid hydroxylation. In contrast, fatty alcohols of the same chain length are exclusively hydroxylated at ω, ω-1, and ω-2 positions. Docking results for the corresponding CYP4B1-substrate complexes revealed that fatty acids can adopt U-shaped bonding conformations, such that carbon atoms in both arms may approach the heme-iron. Quantum chemical estimates of activation energies of the hydrogen radical abstraction by the reactive compound 1 as well as electron densities of the substrate orbitals led to the conclusion that fatty acid and fatty alcohol oxidations by CYP4B1 are kinetically controlled reactions.
Thesseling, Florian A.,Hutter, Michael C.,Wiek, Constanze,Kowalski, John P.,Rettie, Allan E.,Girhard, Marco
(2019/12/12)

Heme-thiolate sulfenylation of human cytochrome P450 4A11 functions as a redox switch for catalytic inhibition
Cytochrome P450 (P450, CYP) 4A11 is a human fatty acid ω-hydroxylase that catalyzes the oxidation of arachidonic acid to the eicosanoid 20-hydroxyeicosatetraenoic acid (20-HETE), which plays important roles in regulating blood pressure regulation. Variants of P450 4A11 have been associated with high blood pressure and resistance to anti-hypertensive drugs, and 20-HETE has both pro- and antihypertensive properties relating to increased vasoconstriction and natriuresis, respectively. These physiological activities are likely influenced by the redox environment, but the mechanisms are unclear. Here, we found that reducing agents (e.g. dithiothreitol and tris(2-carboxyethyl) phosphine) strongly enhanced the catalytic activity of P450 4A11, but not of 10 other human P450s tested. Conversely, added H2O2 attenuated P450 4A11 catalytic activity. Catalytic roles of five of the potentially eight implicated Cys residues of P450 4A11 were eliminated by site-directed mutagenesis. Using an isotope-coded dimedone/iododimedone-labeling strategy and mass spectrometry of peptides, we demonstrated that the heme-thiolate cysteine (Cys-457) is selectively sulfenylated in an H2O2 concentration-dependent manner. This sulfenylation could be reversed by reducing agents, including dithiothreitol and dithionite. Of note, we observed heme ligand cysteine sulfenylation of P450 4A11 ex vivo in kidneys and livers derived from CYP4A11 transgenic mice. We also detected sulfenylation of murine P450 4a12 and 4b1 heme peptides in kidneys. To our knowledge, reversible oxidation of the heme thiolate has not previously been observed in P450s and may have relevance for 20-HETE-mediated functions.
Albertolle, Matthew E.,Kim, Donghak,Nagy, Leslie D.,Yun, Chul-Ho,Pozzi, Ambra,Savas, üzen,Johnson, Eric F.,Guengerich, F. Peter
p. 11230 - 11242
(2017/08/08)

Tandem Reductive Hydroformylation of Castor Oil Derived Substrates and Catalyst Recycling by Selective Product Crystallization
An orthogonal tandem catalytic system consisting of rhodium and ruthenium complexes yielded linear C12 α,ω-bifunctional compounds from commercial, castor oil derived renewable substrates. With aldehyde yields up to 88 % and selectivities to the linear species of up to 95 %, this approach is direct and atom economic and provides easy access to potential polymer precursors for polycondensates. Additionally, a straightforward method for selective product crystallization was developed, which enabled recycling of the tandem catalytic system for two runs with excellent activity and simultaneously provided a high-purity product.
Furst, Marc R. L.,Korkmaz, Vedat,Gaide, Tom,Seidensticker, Thomas,Behr, Arno,Vorholt, Andreas J.
p. 4319 - 4323
(2017/12/15)

Whole-cell microtiter plate screening assay for terminal hydroxylation of fatty acids by P450s
A readily available galactose oxidase (GOase) variant was used to develop a whole cell screening assay. This endpoint detection system was applied in a proof-of-concept approach by screening a focussed mutant library. This led to the discovery of the thus far most active P450 Marinobacter aquaeolei mutant catalysing the terminal hydroxylation of fatty acids.
Weissenborn, Martin J.,Notonier, Sandra,Lang, Sarah-Luise,Otte, Konrad B.,Herter, Susanne,Turner, Nicholas J.,Flitsch, Sabine L.,Hauer, Bernhard
supporting information
p. 6158 - 6161
(2016/05/19)

From Alkanes to Carboxylic Acids: Terminal Oxygenation by a Fungal Peroxygenase
A new heme–thiolate peroxidase catalyzes the hydroxylation of n-alkanes at the terminal position—a challenging reaction in organic chemistry—with H2O2as the only cosubstrate. Besides the primary product, 1-dodecanol, the conversion of dodecane yielded dodecanoic, 12-hydroxydodecanoic, and 1,12-dodecanedioic acids, as identified by GC–MS. Dodecanal could be detected only in trace amounts, and 1,12-dodecanediol was not observed, thus suggesting that dodecanoic acid is the branch point between mono- and diterminal hydroxylation. Simultaneously, oxygenation was observed at other hydrocarbon chain positions (preferentially C2 and C11). Similar results were observed in reactions of tetradecane. The pattern of products formed, together with data on the incorporation of18O from the cosubstrate H218O2, demonstrate that the enzyme acts as a peroxygenase that is able to catalyze a cascade of mono- and diterminal oxidation reactions of long-chain n-alkanes to give carboxylic acids.
Olmedo, Andrés,Aranda, Carmen,del Río, José C.,Kiebist, Jan,Scheibner, Katrin,Martínez, Angel T.,Gutiérrez, Ana
supporting information
p. 12248 - 12251
(2016/10/13)

ALKANE OXIDATION BY MODIFIED HYDROXYLASES
This invention relates to modified hydroxylases. The invention further relates to cells expressing such modified hydroxylases and methods of producing hydroxylated alkanes by contacting a suitable substrate with such cells.
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Paragraph 0339

(2016/02/16)

DIHYDROOROTIC ACID DEHYDROGENASE INHIBITOR
The present invention provides a novel dihydroorotic acid dehydrogenase inhibitor which is applicable to various diseases. When used as an active ingredient, a compound represented by formula (I): (wherein X represents a halogen atom, R1 represents a hydrogen atom, R2 represents an alkyl group containing 1 to 7 carbon atoms, R3 represents -CHO, and R4 represents -CH2-CH=C(CH3)-R0 (wherein R0 represents an alkyl group containing 1 to 12 carbon atoms which may have a substituent on the terminal carbon and/or on a non-terminal carbon, etc.)), an optical isomer thereof or a pharmaceutically acceptable salt thereof has a high inhibitory effect on dihydroorotic acid dehydrogenase and can be used as an immunosuppressive agent, a therapeutic agent for rheumatism, an anticancer agent, a therapeutic agent for graft rejection, an antiviral agent, an anti-H. pylori agent, a therapeutic agent for diabetes or the like.
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(2015/04/15)

NOVEL DIHYDROXYBENZENE DERIVATIVES AND ANTIPROTOZOAL AGENT COMPRISING SAME AS ACTIVE INGREDIENT
Novel compounds below are useful for preventing or treating diseases caused by protozoans. At least one of a compound represented by Formula (I) (wherein, X represents a hydrogen atom or a halogen atom; R1 represents a hydrogen atom; R2 represents a hydrogen atom or a C1-7 alkyl group; R3 represents -CHO, -C(=O)R5, -COOR5 (wherein R5 represents a C1-7 alkyl group), -CH2OH or -COOH; and R4 represents a C1-16 alkyl group having one or more substituents on a terminal carbon atom and/or non-terminal carbon atom(s), a C2-16 alkenyl group having one or more substituents on a terminal carbon atom and/or non-terminal carbon atom(s), or a C2-16 alkynyl group having one or more substituents on a terminal carbon atom and/or non-terminal carbon atom(s)), an optical isomer thereof, and a pharmaceutically acceptable salt is used.
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(2013/09/26)

Tandem decarboxylative hydroformylation-hydrogenation reaction of α,β-unsaturated carboxylic acids toward aliphatic alcohols under mild conditions employing a supramolecular catalyst system
A new atom economic catalytic method for a highly chemoselective reduction of α,β-unsaturated carboxylic acids to the corresponding saturated alcohols under mild reaction conditions, compatible with a wide range reactive functional groups, is reported. The new methodology consists of a novel tandem decarboxylative hydroformylation/aldehyde reduction sequence employing a unique supramolecular catalyst system.
Diab, Lisa,Gellrich, Urs,Breit, Bernhard
supporting information
p. 9737 - 9739
(2013/10/21)

PROCESS FOR PRODUCING DODECANE-1, 12-DIOL BY REDUCTION OF LAURYL LACTONE PRODUCED FROM THE OXIDATION OF CYCLODODECANONE
A process for synthesizing dodecane-1,12-diol, and by-products thereof, by the reduction of lauryl lactone produced from the oxidation of cyclododecanone.
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Paragraph 00131

(2013/08/15)

Direct terminal alkylamino-functionalization via multistep biocatalysis in one recombinant whole-cell catalyst
Direct and regiospecific amino-functionalization of non-activated carbon could be achieved using one recombinant microbial catalyst. The presented proof of concept shows that heterologous pathway engineering allowed the construction of a whole-cell biocatalyst catalyzing the terminal amino-functionalization of fatty acid methyl esters (e.g., dodecanoic acid methyl ester) and alkanes (e.g., octane). By coupling oxygenase and transaminase catalysis in vivo, both substrates are converted with absolute regiospecificity to the terminal amine via two sequential oxidation reactions followed by an amination step. Such demanding chemical three-step reactions achieved with a single catalyst demonstrate the tremendous potential of whole-cell biocatalysts for the production of industrially relevant building blocks. Copyright
Schrewe, Manfred,Ladkau, Nadine,Buehler, Bruno,Schmid, Andreas
supporting information
p. 1693 - 1697
(2013/07/19)

Investigation of the origin and synthetic application of the pseudodilution effect for Pd-catalyzed macrocyclisations in concentrated solutions with immobilized catalysts
Immobilized Pd-complexes allowed macrocyclisations via the Tsuji-Trost-reaction in concentrated solutions. Systematic studies suggest that the origin of this pseudodilution effect is neither film diffusion nor gel diffusion, but the reduction in conformational freedom of intermediates and intramolecular prenucleophile activation. In contrast a pseudodilution effect could not be observed for Sonogashira- and Suzuki-macrocyclisations.
Brehm, Elisabeth,Breinbauer, Rolf
supporting information
p. 4750 - 4756
(2013/07/26)

Bacterial CYP153A monooxygenases for the synthesis of omega-hydroxylated fatty acids
CYP153A from Marinobacter aquaeolei has been identified as a fatty acid ω-hydroxylase with a broad substrate range. Two hotspots predicted to influence substrate specificity and selectivity were exchanged. Mutant G307A is 2- to 20-fold more active towards fatty acids than the wild-type. Residue L354 is determinant for the enzyme ω-regioselectivity.
Honda Malca, Sumire,Scheps, Daniel,Kuehnel, Lisa,Venegas-Venegas, Elena,Seifert, Alexander,Nestl, Bettina M.,Hauer, Bernhard
supporting information; experimental part
p. 5115 - 5117
(2012/06/30)

Flavocytochrome P450 BM3 mutant W1046A is a NADH-dependent fatty acid hydroxylase: Implications for the mechanism of electron transfer in the P450 BM3 dimer
Bacillus megaterium P450 BM3 (BM3) is a P450/P450 reductase fusion enzyme, where the dimer is considered the active form in NADPH-dependent fatty acid hydroxylation. The BM3 W1046A mutant was generated, removing an aromatic "shield" from its FAD isoalloxazine ring. W1046A BM3 is a catalytically active NADH-dependent lauric acid hydroxylase, with product formation slightly superior to the NADPH-driven enzyme. The W1046A BM3 K m for NADH is 20-fold lower than wild-type BM3, and catalytic efficiency of W1046A BM3 with NADH and NADPH are similar in lauric acid oxidation. Wild-type BM3 also catalyzes NADH-dependent lauric acid hydroxylation, but less efficiently than W1046A BM3. A hypothesis that W1046A BM3 is inactive [15] helped underpin a model of electron transfer from FAD in one BM3 monomer to FMN in the other in order to drive fatty acid hydroxylation in native BM3. Our data showing W1046A BM3 is a functional fatty acid hydroxylase are consistent instead with a BM3 catalytic model involving electron transfer within a reductase monomer, and from FMN of one monomer to heme of the other [12]. W1046A BM3 is an efficient NADH-utilizing fatty acid hydroxylase with potential biotechnological applications.
Girvan, Hazel M.,Dunford, Adrian J.,Neeli, Rajasekhar,Ekanem, Idorenyin S.,Waltham, Timothy N.,Joyce, M. Gordon,Leys, David,Curtis, Robin A.,Williams, Paul,Fisher, Karl,Voice, Michael W.,Munro, Andrew W.
experimental part
p. 75 - 85
(2012/03/08)

Calculated and experimental spin state of seleno cytochrome p450
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Jiang, Yongying,Sivaramakrishnan, Santhosh,De Ortiz Montellano, Paul R.,Hayashi, Takahiro,Moenneloccoz, Pierre,Cohen, Shimrit,Shaik, Sason
supporting information; experimental part
p. 7193 - 7195
(2009/12/28)

Solid-phase synthesis of a library of linear oligoester ion-channels
A solid-phase synthesis protocol was used to prepare fifteen new linear tetra-, and penta-esters structurally related to an active lead compound. The structures were assembled from three types of hydroxyl protected building blocks: monoalkyl esters of hydroxyglutaric acid, ω-hydroxyacids, and α-hydroxymethylalkanoic acids. The standard methodology gave acceptable quantities of material free of small molecule impurities. Mass spectrometric analysis revealed the presence of deletions due to incomplete coupling, as well as additions and macrolactones due to partial acidic rearrangement on release from the solid-support. The amount of these impurities could be estimated from the 1H NMR spectra, and their implications for subsequent activity analysis are discussed.
Fyles, Thomas Murray,Luong, Horace
experimental part
p. 725 - 732
(2009/06/19)

Bioreversible derivatives of phenol. 2. Reactivity of carbonate esters with fatty acid-like structures towards hydrolysis in aqueous solutions
A series of model phenol carbonate ester prodrugs encompassing derivatives with fatty acid-like structures were synthesized and their stability as a function of pH (range 0.4-12.5) at 37°C in aqueous buffer solutions investigated. The hydrolysis rates in aqueous solutions differed widely, depending on the selected pro-moieties (alkyl and aryl substituents). The observed reactivity differences could be rationalized by the inductive and steric properties of the substituent groups when taking into account that the mechanism of hydrolysis may change when the type of pro-moiety is altered, e.g. n-alkyl vs. t-butyl. Hydrolysis of the phenolic carbonate ester 2-(phenoxycarbonyloxy)-acetic acid was increased due to intramolecular catalysis, as compared to the derivatives synthesized from ω-hydroxy carboxylic acids with longer alkyl chains. The carbonate esters appear to be less reactive towards specific acid and base catalyzed hydrolysis than phenyl acetate. The results underline that it is unrealistic to expect that phenolic carbonate ester prodrugs can be utilized in ready to use aqueous formulations. The stability of the carbonate ester derivatives with fatty acid-like structures, expected to interact with the plasma protein human serum albumin, proved sufficient for further in vitro and in vivo evaluation of the potential of utilizing HSA binding in combination with the prodrug approach for optimization of drug pharmacokinetics.
stergaard, Jesper,Larsen, Claus
p. 2396 - 2412
(2008/02/14)

Molecular cloning of CYP76B9, a cytochrome P450 from Petunia hybrida, catalyzing the ω-hydroxylation of capric acid and lauric acid
A cDNA encoding a cytochrome P450 (CYP76B9) was isolated from Petunia hybrida. Northern blot analysis revealed preferential expression of the gene in flowers and leaves. The recombinant yeast microsomes expressing CYP76B9 was allowed to react with capric acid and lauric acid as substrates. One major metabolite was produced from each fatty acid after incubation with yeast microsomes expressing CYP76B9. The metabolites were identified by gas chromatography-mass spectrometry (GC-MS) as ω-hydroxy capric acid and ω-hydroxy lauric acid. The kinetic parameters of the reactions were K m = 9:4 μM and Vmax = 13:6 mol min-1 per mol of P450 for capric acid, and Km = 5:7 μM and Vmax = 19:1 mol min-1 per mol of P450 for lauric acid. We found that the ω-hydroxy metabolites of capric acid and lauric acid can affect the plant growth of Arabidopsis thaliana. Plants grown in the presence of ω-hydroxy fatty acids exhibited shorter root length than control plants with the corresponding non-hydroxylated fatty acids.
Imaishi, Hiromasa,Petkova-Andonova, Mariana
p. 104 - 113
(2008/03/13)

Simple preparation of highly pure monomeric ω-hydroxycarboxylic acids
Highly pure monomeric ω-hydroxycarboxylic acids (HCAs) with ≥C6 are prepared from their corresponding lactones or alkyl ω-hydroxycarboxylates through saponification followed by H 2SO4 acidification and treatment at 35-40 °C/8-12 mbar or by freeze-drying. The HCA is being formed through its sodium or potassium salt and is obtained in 80-85% yield with >99.5% purity, uncontaminated with dimers. This simple procedure excludes chromatographic purification.
Stephan, Michel Massoud S.,Mohar, Barbara
p. 481 - 483
(2012/12/22)

A self-sufficient peroxide-driven hydroxylation biocatalyst
Directed evolution of the heme domain of cytochrome P450 BM-3 has resulted in a versatile, highly active peroxide-driven hydroxylation catalyst (see picture) that requires neither NADPH nor reductase and functions in a cell-free reaction system. This simplified, biomimetic catalyst is amenable to further optimization, for example, to improve stability or alter its substrate range.
Cirino, Patrick C.,Arnold, Frances H.
p. 3299 - 3301
(2007/10/03)

Enhanced electron transfer and lauric acid hydroxylation by site-directed mutagenesis of CYP119
CYP119, a cytochrome P450 from a thermophilic organism for which a crystal structure is available, is shown here to hydroxylate lauric acid in a reaction supported by putidaredoxin and putidaredoxin reductase. This fatty acid hydroxylation activity is increased 15-fold by T214V and D77R mutations. The T214V mutation increases the rate by facilitating substrate binding and enhancing the associated spin state change, whereas the D77R mutation improves binding of the heterologous redox partner putidaredoxin to CYP119 and the rate of electron transfer from it to the heme group. A sequence alignment with P450cam can, therefore, be used to identify a part of the binding site for putidaredoxin on an unrelated P450 enzyme. This information can be used to engineer by mutagenesis an improved complementarity of the protein-protein interface that results in improved electron transfer from putidaredoxin to the P450 enzyme. As a result, the catalytic activity of the thermo- and barostable CYP119 has been incorporated into a catalytic system that hydroxylates fatty acids.
Koo, Laura S.,Immoos, Chad E.,Cohen, Michael S.,Farmer, Patrick J.,Ortiz de Montellano, Paul R.
p. 5684 - 5691
(2007/10/03)

Simplified syntheses of polymerizable bis-substituted phosphatidylcholines with various chain lengths
Syntheses of new compounds, 1,2-bis[15-(2',4'-hexadienoyloxy)pentadecanoyl]- and 1,2-bis[15-(2',4'-hexadienoyloxy)dodecanoyl]-sn-glycero-3-phosphatidylcholine s, via a simplified procedure are reported. The new approach utilizes the conversion of commercially available lactones into polymerizable bis-substituted phosphatidylcholines after two steps of reaction. (C) 2000 Elsevier Science Ltd.
Bae,Kim,Kim,Koo,Ryeom,Ryeom,Fu,Chang
p. 8495 - 8498
(2007/10/03)

Effects of arachidonic acid, prostaglandins, retinol, retinoic acid and cholecalciferol on xenobiotic oxidations catalysed by human cytochrome P450 enzymes
1. Effects of arachidonic acid, prostaglandins, retinol, retinoic acid and cholecalciferol on xenobiotic oxidations catalysed by 12 recombinant human cytochrome P450 (P450 or CYP) enzymes and by human liver microsomes have been investigated. 2. Arachidonic acid (50 μM) significantly inhibited CYP1A1- and 1A2-dependent 7-ethoxycoumarin O-deethylations, CYP2C8-dependent taxol 6α-hydroxylation and CYP2C19-dependent R-warfarin 7-hydroxylation. This chemical also inhibited slightly the xenobiotic oxidations catalysed by CYP1B1, 2B6, 2C9, 2D6, 2E1 and 3A4 in recombinant enzyme systems. 3. Retinol, retinoic acid and cholecalciferol were strong inhibitors for xenobiotic oxidations catalysed by recombinant CYP1A1, 2C8 and 2C19. 4. Dixon plots of inhibitions of CYP1A1-, 1A2-, 2C8- and 2C19-dependent xenobiotic oxidations by arachidonic acid, of CYP1A1-, 2B6- and 2C19-dependent activities by retinol, and of CYP1A1- and 2C19-dependent activities by cholecalciferol indicated that these chemicals inhibit P450 activities mainly through a competitive mechanism. 5. In human liver microsomes, arachidonic acid inhibited CYP1A2-dependent theophylline hydroxylation, CYP2C8-dependent taxol 6α-hydroxylation and CYP2C19-dependent omeprazole 5-hydroxylation. Taxol 6α-hydroxylation was also inhibited by retinol and retinoic acid, and omeprazole 5-hydroxylation was inhibited by retinol in human liver microsomes. 6. These results suggest that xenobiotic oxidations by P450 enzymes are affected by endobiotic chemicals and that the endobiotic-xenobiotic interactions as well as drug-drug interactions may be of great importance when understanding the basis for pharmacological and toxicological actions of a number of xenobiotic chemicals.
Yamazaki,Shimada
p. 231 - 241
(2007/10/03)

Preparation of ω-hydroxy acids by reduction of α,ω-methylene diesters with NaBH4
By reaction of the dicesium salts of long chain dicarboxylic acids (C atoms > 9) with methylene iodide the corresponding methylene diesters were prepared. These acylals, by reduction with NaBH4 in THF, give the corresponding ω-hydroxy acids.
Benitez, Pilar,Delgado, Ana,Farrera, Joan-Anton,Ribo, Josep M.
p. 1697 - 1702
(2007/10/03)

Process of preparing ω-hydroxy acids
A new synthesis of ω-hydroxy acids, which employs commercially available starting materials and lowers the cost of production. The process involves coupling a fatty acyl group by enamine chemistry, followed by a ring expansion and selective reduction of ketoacid.
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(2008/06/13)

Process for producing ω-hydroxy fatty acids
ω-Hydroxy fatty acids usable for the synthesis of medicaments, perfumes and polymers are produced by subjecting an alkali or alkaline earth metal salt of long-chain dicarboxylic acid monoester to a reduction with a borohydride compound or catalytic hydrogenating reduction treatment.
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(2008/06/13)

Lactones. 2. Enthalpies of hydrolysis, reduction, and formation of the C4-C13 monocyclic lactones. Strain energies and conformations
The enthalpies of hydrolysis of the monocyclic lactones from γ-butyrolactone to tridecanolactone were determined calorimetrically, and the acyclic ethyl having the number of atoms were studied in the fashion. The enthalpies of reduction of the lactones to the corresponding α,ω-alkanediols with lithium triethylborohydride also were determined. The enthalpies of formation of the lactones and the ethyl esters were derived from these data. They were converted to values for the gas phase by measuring the enthalpies of vaporization of ethyl esters and of lactones. In the of γ-butyrolactone and δ-valerolactone, the enthalpies of formation were in good accord with the previously reported values determined via combustion calorimetry. The strain energies of the lactones were obtained via isodesmic reactions. Valerolactone had a strain energy of 11 kcal/mol, and the largest strain energy was found with octanolactone (13 kcal/mol). The conformations of γ-butyrolactone and δ-valerolactone were studied via MP2/6-31G* geometry optimizations, and the conformations of the other lactones were studied with use of the molecular mechanics program MM3. The energies of the lactones estimated via molecular mechanics were compared with the experimental results.
Wiberg, Kenneth B.,Waldron, Roy F.
p. 7697 - 7705
(2007/10/02)

Process for producing omega-hydroxy fatty acids
ω-Hydroxy fatty acids usable for the synthesis of medicaments, perfumes and polymers are produced by subjecting an alkali or alkaline earth metal salt of long-chain dicarboxylic acid monoester to a reduction with a borohydride compound or catalytic hydrogenating reduction treatment.
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(2008/06/13)

Synthesis of even C24-C30 primary normal aliphatic alcohols from cyclododecanone
A simple method has been developed for the oxidation of cyclododecanone by sodium persulfate in an aqueous methanol solution of sulfuric acid to give 12-hydroxydodecanoic acid, which upon treatment with HBr in acetic acid gives 12-bromododecanoic acid with RMgX, where R=C12H25, C14H29, C16H33, and C18H37 in THF in the presence of Li2CuCl4 and subsequent reduction of the salts of the alkanecarboxylic acids by LiAlH4 give primary even normal C24-C30 alcohols.
Zakharkin, L. I.,Churilova, I. M.,Anikina, E. V.
p. 65 - 67
(2007/10/02)

Model Studies on the Synthesis of Medium-sized and Large Carbocycles using the Ireland Enolate Claisen Rearrangement
Model studies have shown that the enolate Claisen rearrangement, a modification (developed by R.E.Ireland et al.) of the original Claisen rearrangement, can successfully be applied to the elaboration of medium-sized and large carbocycles from O-silyl enolates of suitable unsaturated macrolides (Scheme).The rearrangements are largely non-stereoselective, a fact which can be rationalised in terms of the intermediacy of both chair- and boat-like transition states and possibly because, in some cases, both the (E)- and (Z)-enolate of the macrolides are involved.
Cameron, Andrew G.,Knight, David W.
p. 161 - 168
(2007/10/02)

Studies on Fermantation Products and Metabolism of Long Chain Alkyl Diamine in Microorganisms
Ten bacteria capable of using 1,12-diaminododecane (DAD) as a sole carbon and energy source were isolated from soil samples.Four strains (K95, K55, K24, 110-2)were identified as Pseudomonas, four (DAD2-3, 10-23-A, 10-23-B, K61) as Nocardia and two (DAD2-1, 1994) as Corynebacterium on the basis of their taxonomic characteristics.Metabolic products such as 12-aminododecanoic acid, 12-hydroxydodecanoic acid, 1,10-decanedicarboxylic acid, sebacic acid, suberic acid, adipic acid and α-ketoglutaric acid were found in the culture broths of various bacteria.The yields of 12-aminododecanoic acid and 12-hydroxydodecanoic acid from DAD were as high as 55 percent and 20 percent, respectively.An amine dehydrogenase was found in cell-free extracts of Pseudomonas K95 and amine oxydases were detected in cell-free extracts of Nocardia 10-23-A.A biodegradation pathway for DAD is proposed.
Niimura, Youichi,Yinbo, Qu,Lee, Sang-Joon,Omori, Toshio,Minoda, Yasuji
p. 1437 - 1444
(2007/10/02)

Convenient Syntheses of Bifunctional C12-Acyclic Compounds from Cyclododecanone
The conversion of cyclododecanone by convenient, non-hazardous, and high-yielding reactions into a set of useful C12-bifunctional intermediates is described.Baeyer-Villiger oxidation and hydrolysis give a hydroxy acid, successively converted into the bromo acid, bromo alcohol, crude bromo aldehyde, pure bromo aldehyde ethylene acetal, and pure bromo aldehyde.Preferred reagents for the transformation CO2H -> CHO are borane-dimethyl sulphide followed by dimethyl sulphoxide-oxalyl dichloride-triethylamine.
Bidd, Ilesh,Kelly, David J.,Ottley, Peter M.,Paynter, Oliver I.,Simmonds, Derek J.,Whiting, Mark C.
p. 1369 - 1372
(2007/10/02)

The Synthesis of Long-chain Unbranched Aliphatic Compounds by Molecular Doubling
A convenient general synthesis, applicable to alkanes and terminally mono- and di-substituted alkanes of any chain length, is described; cyclododecanone is used as the starting material, and the C12 chain is doubled in length as often as required and adjusted first to a multiple of 12, and then to any desired length.
Paynter, Oliver I.,Simmonds, Derek J.,Whiting, Mark C.
p. 1165 - 1166
(2007/10/02)

Triphase Catalytic Cyclization. Efficacious Macrolide Synthesis
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Regen, Steven L.,Kimura, Yoshikazu
p. 2064 - 2065
(2007/10/02)

Oxidation of Hydrazines with Benzeneseleninic Acid and Anhydride
Benzeneseleninic acid (1) and anhydride (2) oxidize hydrazine or 1,2-disubstituted derivatives to corresponding diazenes.Hydrazides afford selenoesters 4, N,N'-diacyl- or diaroylhydrazines 5, and carboxylic acids.Benzeneselenenic acid (7) is a required intermediate in selenoester formation and may be generated independently by the reaction of triphenylphosphine with 1.Selenoesters are efficiently prepared by the slow addition of a mixture of the hydrazide and triphenylphosphine to 1 in dichloromethane solution.Polar solvents are unsuitable.Inverse addition provides compounds 5 as major products.Oxidation of hydrazides of structure HO-(CH2)nCONHNH2 gives the corresponding selenoesters 14 and acids 16 when n=11 or 14 lactones 17 and 18 when n=4 or 3.Arylhydrazines react with 1 or 2 to furnish arenes 23 and aryl phenyl selenides 24.
Back, Thomas G.,Collins, Scott,Ker, Russell G.
p. 1564 - 1570
(2007/10/02)