- MANUFACTURING METHOD OF β-HYDROXYLACTONE (METH)ACRYLIC ACID ESTER
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PROBLEM TO BE SOLVED: To provide a method capable of manufacturing (meth)acrylic acid ester of β-hydroxylactone at high yield with almost no side reaction. SOLUTION: The problem is solved by a manufacturing method of β-hydroxylactone (meth)acrylic acid ester for providing corresponding (meth)acrylic acid ester by reacting specific β-hydroxylactone (B) and at least one kind of acid anhydride (C) selected from (meth)acrylic acid anhydride (C1) and anhydride of (meth)acrylic acid and carboxylic acid other than the (meth)acrylic acid (C2) in presence of a specific Lewis acid catalyst (A). SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0045; 0049-0051
(2020/01/23)
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- Method for preparing mevalonolactone from biosynthesized mevalonic aicd using phosphoric acid
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The present invention refers to a method using a phosphoric acid bath disclosure number [...] maul proposal it buys preformed biosynthesis from each other. The present invention refers to any impurities can be obtained have a high purity [...] effect. (by machine translation)
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Paragraph 0038; 0040; 0046
(2018/08/02)
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- METHODS OF FORMING DIOL COMPOUNDS
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Methods of forming a C4 to C7 diol compound, the methods including a first step of reacting a C4 to C7 dicarboxylic acid with hydrogen (H2) gas on a first heterogeneous catalyst at a first temperature and a first pressure to form a C4 to C7 lactone; and a subsequent step of reacting the lactone with hydrogen (H2) gas on a second heterogeneous catalyst at a second temperature and a second pressure, wherein the second temperature is lower than the first temperature. Also disclosed are methods of forming a solvent, the methods including reacting a C4 to C7 dicarboxylic acid with hydrogen (H2) gas on a first heterogeneous catalyst at a first temperature and a first pressure to form a solvent. Further disclosed herein are methods that include reacting mevalonolactone with hydrogen (H2) gas on a second heterogeneous catalyst at a second temperature and a second pressure to form a diol compound.
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Paragraph 0094
(2017/11/06)
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- PROCESSES FOR CONVERSION OF BIOLOGICALLY DERIVED MEVALONIC ACID
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The invention relates to a process comprising reacting mevalonic acid, or a solution comprising mevalonic acid, to yield a first product or first product mixture, optionally in the presence of a solid catalyst and/or at elevated temperature and/or pressure. The invention further relates to a process comprising: (a) providing a microbial organism that expresses a biosynthetic mevalonic acid pathway; (b) growing the microbial organism in fermentation medium comprising suitable carbon substrates, whereby biobased mevalonic acid is produced; and (c) reacting said biobased mevalonic acid to yield a first product or first product mixture.
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Paragraph 0094
(2016/06/13)
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- Efficient and Selective Cu/Nitroxyl-Catalyzed Methods for Aerobic Oxidative Lactonization of Diols
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Cu/nitroxyl catalysts have been identified that promote highly efficient and selective aerobic oxidative lactonization of diols under mild reaction conditions using ambient air as the oxidant. The chemo- and regioselectivity of the reaction may be tuned by changing the identity of the nitroxyl cocatalyst. A Cu/ABNO catalyst system (ABNO = 9-azabicyclo[3.3.1]nonan-N-oxyl) shows excellent reactivity with symmetrical diols and hindered unsymmetrical diols, whereas a Cu/TEMPO catalyst system (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl) displays excellent chemo- and regioselectivity for the oxidation of less hindered unsymmetrical diols. These catalyst systems are compatible with all classes of alcohols (benzylic, allylic, aliphatic), mediate efficient lactonization of 1,4-, 1,5-, and some 1,6-diols, and tolerate diverse functional groups, including alkenes, heterocycles, and other heteroatom-containing groups.
- Xie, Xiaomin,Stahl, Shannon S.
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p. 3767 - 3770
(2015/04/14)
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- Quaternary Stereogenic Centers through Enantioselective Heck Arylation of Acyclic Olefins with Aryldiazonium Salts: Application in a Concise Synthesis of (R)-Verapamil
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We describe herein a highly regio- and enantioselective Pd-catalyzed Heck arylation of unactivated trisubstituted acyclic olefins to provide all-carbon quaternary stereogenic centers. Chiral N,N ligands of the pyrimidine- and pyrazino-oxazoline class were developed for that purpose, providing the desired products in good to high yields with enantiomeric ratios up to >99:1. Both linear and branched substituents on the olefins were well-tolerated. The potential of this new method is demonstrated by the straightforward synthesis of several O-methyl lactols and lactones containing quaternary stereocenters, together with a concise enantioselective total synthesis of the calcium channel blocker verapamil.
- Oliveira, Caio C.,Pfaltz, Andreas,Correia, Carlos Roque Duarte
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supporting information
p. 14036 - 14039
(2016/01/25)
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- Synthesis of mevalonate-and fluorinated mevalonate prodrugs and their in vitro human plasma stability
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The mevalonate pathway is essential for the production of many important molecules in lipid biosynthesis. Inhibition of this pathway is the mechanism of statin cholesterol-lowering drugs, as well as the target of drugs to treat osteoporosis, to combat parasites, and to inhibit tumor cell growth. Unlike the human mevalonate pathway, the bacterial pathway appears to be regulated by diphosphomevalonate (DPM). Enzymes in the mevalonate pathway act to produce isopentenyl diphosphate, the product of the DPM decarboxylase reaction, utilize phosphorylated (charged) intermediates, which are poorly bioavailable. It has been shown that fluorinated DPMs (6-fluoro-and 6,6,6-trifluoro-5-diphosphomevalonate) are excellent inhibitors of the bacterial pathway; however, highly charged DPM and analogs are not bioavailable. To increase cellular permeability of mevalonate analogs, we have synthesized various prodrugs of mevalonate and 6-fluoro-and 6,6,6-trifluoromevalonate that can be enzymatically transformed to the corresponding DPM or fluorinated DPM analogs by esterases or amidases. To probe the required stabilities as potentially bioavailable prodrugs, we measured the half-lives of esters, amides, carbonates, acetals, and ketal promoieties of mevalonate and the fluorinated mevalonate analogs in human blood plasma. Stability studies showed that the prodrugs are converted to the mevalonates in human plasma with a wide range of half-lives. These studies provide stability data for a variety of prodrug options having varying stabilities and should be very useful in the design of appropriate prodrugs of mevalonate and fluorinated mevalonates.
- Kang, Soosung,Watanabe, Mizuki,Jacobs,Yamaguchi, Masaya,Dahesh, Samira,Nizet, Victor,Leyh, Thomas S.,Silverman, Richard B.
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p. 448 - 461
(2016/10/19)
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- A catalytic enantioselective route to hydroxy-substituted quaternary carbon centers: Resolution of tertiary aldols with a catalytic antibody
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Aldolase antibody 38C2-catalyzed resolutions of tertiary aldols were studied. Tertiary aldols proved to be very good substrates for antibody catalyzed retro-aldol reactions. The catalytic proficiency, (k(cat)/K(M))/k(uncat), of the antibody for these reactions was on the order of 1010 M-1. A fluorogenic tertiary aldol allowed for the quantitative study of enantiomeric excess as a function of reaction conversion, revealing an E value of ca. 160 in this case. Study of a variety of substrates demonstrated that antibody-catalyzed retro-aldolization provides rapid entry to highly enantiomerically enriched tertiary aldols, typically > 95% ee, containing structurally varied, heteroatom-substituted quaternary carbon centers. The utility of this approach to natural product syntheses has been demonstrated with the syntheses of (+)-frontalin, the side chain of Saframycin H, and formal syntheses of (+)- and (-)-mevalonolactone.
- List, Benjamin,Shabat, Doron,Zhong, Guofu,Turner, James M.,Li, Anthony,Bui, Tommy,Anderson, James,Lerner, Richard A.,Barbas III, Carlos F.
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p. 7283 - 7291
(2007/10/03)
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- Synthesis of lactones via the oxidation of α,ω-diols with sodium bromite and alumina under water free conditions
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Oxidation of α,ω-diols with sodium bromite can be readily performed in dichloromethane to afford lactones in fair good yield under mild and neutral conditions with the aid of chromatographic acidic alumina.
- Hirano, Masao,Yakabe, Shigetaka,Morimoto, Takashi
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p. 123 - 130
(2007/10/03)
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- Oxidation of Alcohols with Peracetic Acid in Ethyl Acetate in the Presence of Sodium Bromide
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Aliphatic primary alcohols and 1,ω-diols were oxidized to the dimeric esters and lactones, respectively, by peracetic acid in ethyl acetate in the presence of sodium bromide under mild conditions.Aliphatic secondary and benzylic alcohols were converted smoothly to the corresponding carbonyl compounds by the same system.
- Morimoto, Takashi,Hirano, Masao,Hamaguchi, Takayoshi,Shimoyama, Masahide,Zhuang, Xiumin
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p. 703 - 706
(2007/10/02)
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- SYNTHESIS OF MEVALONOLACTONE FROM 4-(β-HYDROXYETHYL)-4-METHYL-1,3-DIOXANE
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A method has been developed for obtaining mevalonolactone and 3-hydroxy-3-methylglutaric acid from an industrial waste, 4-(β-hydroxyethyl)-4-methyl-1,3-dioxane.
- Sargsyan, M. S.,Manukyan, A. T.,Mkrtumyan, S. A.,Gevorkyan, A. A.
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- Studies on the biosynthesis of the mycotoxin austin, a meroterpenoid metabolite of Aspergillus ustus
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Incorporations of 13C-labelled acetates and methionine into the mycotoxin austin in cultures of Aspergillus ustus give a labelling pattern consistent with a mixed polyketide-terpenoid pathway. Incorporations of 14C and 2H labelled 3,5-dimethylorsellinate confirm the intermediacy of a preformed tetraketide-derived phenolic precursor. Further information on the mechanisms involved in the modifications of both the farnesyl- and tetraketide-derived portions of the molecule are provided by incorporation studies with [1-13C,18O2]acetate, [methyl-13C,2H3]methionine, 13C,18O-labelled dimethylorsellinate, 18O2 gas and [6-13C,6-2H3]mevalonic acid lactone.
- Ahmed,Scott,Stenzel,Simpson,Moore,Trimble,Arai,Vederas
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p. 807 - 816
(2007/10/02)
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- A New Flexible Synthesis of (R,S)-Mevalonolactone
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By selective ozonolysis of the diene (5), a new synthesis of (R,S)-mevalonolactone (1a) has been developed, which can be adapted to other compounds related to (1a).This has been exemplified by the synthesis of the monodeuteriated triol (4d) and dideuteriated mevalonolactone (1d).
- Ferraboschi, Patrizia,Canevotti, Renato,Grisenti, Paride,Santaniello, Enzo
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p. 2301 - 2304
(2007/10/02)
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- PROTECTION OF ALCOHOLS AS THEIR (p-METHOXYBENZYLOXY)METHYL ETHERS.
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Protection of even tertiary alcohols can be accomplished by treatment with p-methoxybenzyl chloromethyl ether.Deprotection can be effected under mild conditions using the DDQ reaction conditions described by Oikawa.
- Kozikowski, Alan P.,Wu, Jiang-Ping
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p. 5125 - 5128
(2007/10/02)
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- An Asymmetric Synthesis of Lactones from Cyclic Acid Anhydrides with Chiral Binaphthyldiamines
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Asymmetric ring opening of the cyclic acid anhydrides cis-2,3-6 with the axially dissymmetric binaphthyldiamines (S)-1a-d and subsequent esterification gave diastereomeric mixtures of the amide-esters 7a-h.Successive reduction of the ester group and ring closure by hydrolysis afforded (-)-cis-2,4-dimethyl-δ-valerolactone (8, 92percent e.e.), (-)-mevalonolactone (9, 58percent e.e.)(+)-3-isopropyl-δ-valerolactone (10, 42percent e.e.), and (+)-2,3-methylene-γ-butyrolactone (11, 46percent e.e).Through kinetic resolution of the racemic anhydride trans-2, (-)-trans-2,4-dimethyl-δ-valerolactone (12) was yielded in a 74percent e.e., whose absolute configuration was established to be 2R,4R.
- Kawakami, Yukio,Hiratake, Jun,Yamamoto, Yukio,Oda, Jun'ichi
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p. 693 - 698
(2007/10/02)
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- Studies on a Synthesis of (RS)-Mevalonic Acid Lactone
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Full details of a high yielding synthesis of mevalonic acid lactone (1) which is of particular value in the preparation of 3- and/or 3'-labelled compounds are described.The key step, conversion of 3-hydroxy-3-methylpentane-1,5-dioic acid (3) into 3-hydroxy-3-methylpentane-1,5-dioic anhydride (4) using acetic anhydride, has been fully investigated, and an additional method using acetyl chloride and triethylamine is described.
- Bardshiri, Esfandiar,Simpson, Thomas J.,Scott, A. Ian,Shishido, Kozo
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p. 1765 - 1767
(2007/10/02)
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- Synthesis of Epoxytrichothecenes: Verrucarin J and Verrucarin J Isomers
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A five-step synthesis of verrucarin J (1) from verrucarol (2) is described.Esterification of (E)-21 and 2 with DDC in the presence of catalytic DMAP was highly regioselective but afforded a 3-4:1 mixture of (E)-23 and the corresponding Z olefin isomer.Two routes from (E)-23 to seco acid 13 are described, the most efficient of which involves the coupling of (E)-24 ("verrol") with muconate ester 28.Macrolactonization of seco acid 13 via mixed anhydride 31 afforded 55-60percent of 1 together with 25-30percent of E,E,E isomer 32.Although attempts to suppress the formation of 32were unsuccessful, treatment of 32 with I2 in C6H6 effected clean isomerization to a 2:1 mixture of 1 and E,Z,E isomer 33.The overall yield of verrucarin J from verrucarol, after a recycle of 32, was 27-30percent .Also described are syntheses of (Z,E,Z)-verrucarin (40) and Z,E,E isomer 41.Verrucarins 1 and 40 are nearly equipotent in the in vitro L1210 mouse leukemia assay, but the (E,E)-muconate isomers 32 and 41 are less active by an order of magnitude.These data may reflect the solvolytic reactivity of 32 and 41, since these compounds rapidly transesterify in EtOH.Seco acid 13 was essentially inactive in the L1210 assay.
- Roush, William R.,Blizzard, Timothy A.
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p. 1772 - 1783
(2007/10/02)
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- Reinvestigation of a Synthesis of (R,S)-Mevalonolactone
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An n.m.r. study of the reaction of 3-hydroxy-3-methylpentane-1,5-dioic acid (5) with excess of acetic anhydride is described.It has shown that 3-hydroxy-3-methylpentane-1,5-dioic acid anhydride (2), previously described by Scott and Shishido as an intermediate in their synthesis of mevalonolactone, is formed only transiently, along with 3-acetoxy-3-methylpentane-1,5-dioic acid (6).Both intermediates eventually give 3-acetoxy-3-methylpentane-1,5-dioic acid anhydride (3).To obtain (R,S)-mevalonolactone, sodium borohydride reduction of 3-hydroxy-3-methylpentane-1,5-dioic acid anhydride (2), prepared from the diacid (5) and N,N-dicyclohexylcarbodi-imide, is shown to be better than reduction of 3-acetoxy-3-methylpentane-1,5-dioic acid anhydride (3).
- Lewer, Paul,MacMillan, Jake
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p. 1417 - 1420
(2007/10/02)
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- Oxidation of Diols to Lactones: A Simple Synthesis of (+/-)-Mevalonolactone
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Oxidation of 1,4-diol and 1,5-diol with pyridinium chlorochromate or chromium(V) reagent yields γ- and δ-lactones respectively in good yields.The mildness of this method has been tested succesfully in a simple synthesis of (+/-)-mevalonolactone (7).
- Chakraborty, T. K.,Bhushan, Vidya,Chandrasekaran, S.
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- Synthesis of (+/-)-Lineatin, an Aggregation Pheromone of Trypodendron lineatum
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A regioselective synthesis of lineatin (1) was accomplished, starting from anhydromevalonolactone (8).Photochemical cycloaddition of 8 with acetylene gave the cyclobutene 9, which was converted to lactone 13 upon methylation followed by oxidation.Hydroboration-oxidation of 13 afforded a mixture of 14 and 15, from which tosylate 18 was obtained.Reduction of 18 gave the endo hemiacetal 19, which underwent an intramolecular displacement to produce 1.Isolineatin (2) was obtained by reduction of 13 to hemiacetal 20, followed by intramolecular oxymercuration with mercuric pivalate and reduction with sodium borohydride.
- White, James D.,Avery, Mitchell A.,Carter, J. Paul
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p. 5486 - 5489
(2007/10/02)
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- CHIRALITY OF THE ACYL GROUP OF β-HYDROXY-β-METHYLGLUTARYLHYDROXYABSCISIC ACID
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The β-carbon of the acyl group of β-hydroxy-β-methylglutarylhydroxyabscisic acid was shown to possess R-configuration by HPLC analysis of the reduced product. - Keywords: Robina pseudacacia; Leguminosae; β-hydroxy-β-methylglutarylhydroxyabscisic acid; chirality; optical resolution; mevalonolactone.
- Hirai, Nobuhiro,Koshimizu, Koichi
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p. 1867 - 1870
(2007/10/02)
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- An Easy Synthesis of (RS)-Mevalonic Acid Lactone
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A high-yielding synthesis of mevalonic acid lactone is described which is of particular value in the preparation of 3' labelled compounds.
- Scott, A. Ian,Shishido, Kozo
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p. 400 - 401
(2007/10/02)
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