76420-07-0Relevant articles and documents
PRODUCTION METHOD FOR CYCLOPENTENONE DERIVATIVE
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Paragraph 0035, (2021/01/29)
[Problem] The present invention provides an industrially-preferable, cost-efficient, low-cost production method for 4-hydroxy-2-hydroxymethyl-2-cyclopenten-1-one (a compound represented by formula (I)) useful as a medicine, an agricultural chemical, or a raw material or intermediate of a medicine, an agricultural chemical, or the like. [Solution] According to the present invention, this compound represented by formula (I) is produced by subjecting an easily available compound represented by formula (II) (tri-O-acetyl-D-glucal) to a heating reaction in pressurized water.
Formation of five-membered carbocycles from D-glucose: A Concise Synthesis of 4-Hydroxy-2-(hydroxymethyl)cyclopentenone
Koseki, Yoshitaka,Watanabe, Toshihiro,Kamishima, Takaaki,Kwon, Eunsang,Kasai, Hitoshi
, p. 1324 - 1328 (2019/09/18)
A concise synthesis of 4-hydroxy-2-(hydroxymethyl)cyclo-pentenone (1) has been accomplished from D-glucose by a three-step sequence that features a catalyst-free hydrothermal reaction of D-glucal, which is readily obtained from D-glucose. Optimization of the reaction conditions for synthesizing 1 was performed by changing the temperature and reaction time. The treatment of D-glucal under the optimal conditions, i.e., at 120 °C for 24 h, provided 1 in the highest isolated yield of 61%. 1 would become a versatile intermediate for the synthesis of various fine chemicals having a cyclopentenone structure from cellulosic biomass.
PRODUCTION METHOD OF OPTICALLY ACTIVE CYCLOPENTENONE DERIVATIVE
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Paragraph 0025; 0026; 0027; 0028; 0029; 0030; 0031, (2019/09/20)
PROBLEM TO BE SOLVED: To provide a production method of an optically active cyclopentenone derivative. SOLUTION: A production method of an optical active material is provided, including optical resolution of a compound of formula (I) by use of a high-speed liquid chromatograph mounting a chiral column. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
One-Step conversion to a disubstituted cyclopentenone from 2-Deoxy-D-Glucose and application to synthesis of prostaglandin e1 methyl ester
Kamishima, Takaaki,Nonaka, Toshiyuki,Watanabe, Toshihiro,Koseki, Yoshitaka,Kasai, Hitoshi
supporting information, p. 1691 - 1696 (2018/11/27)
We have developed a facile one-step conversion of 2-deoxy-D-glucose to form a disubstituted cyclopentenone through catalyst-free hydrothermal reaction under mild conditions. The use of 2-deoxy-D-glucose in one-pot conversion is to provide the formation of a carbon five-membered ring instead of the common biomass-derived furans such as furfural, 5-HMF, etc. The cyclopentenone has a potential to be a building block for the preparation of chemical products. As one example, we successfully demonstrated the synthesis of prostaglandin E1 methyl ester.
Formal synthesis of merrilactone a using a domino cyanide 1,4-addition-aldol cyclization
Nazef, Naim,Davies, Robert D. M.,Greaney, Michael F.
, p. 3720 - 3723 (2012/08/28)
A formal synthesis of merrilactone A has been completed using a domino 1,4-addition-aldol process as the key step. Both iodo- and cyano-1,4-addition- aldol cyclizations were productive in forming the highly hindered C1-C9 bond linking vic-quaternary and tertiary stereocenters. The latter method was used to complete a formal total synthesis of the natural product.
Studies Related to Cyclopentanoid Natural Products. Part 2. An Improved Route to (4R)-4-Hydroxy-2-hydroxymethylcyclopent-2-en-1-one and its O-Substituted Derivatives
Elliott, John D.,Kelson, Andrew B.,Purcell, Neil,Stoodley, Richard J.,Palfreyman, Malcolm N.
, p. 2441 - 2449 (2007/10/02)
(3R,4S,5R)-3,4-O-Cyclohexylidene-3,4,5-trihydroxycyclohexan-1-one (11a), prepared from D-quinic acid (4a) by a published three-step sequence, was converted into the 5-O-benzoyl derivative (11b) by the action of benzoyl chloride.Simultaneous protection of the ketonic carbonyl group and removal of the cyclohexylidene moiety occurred when the compound (11b) was treated with ethane-1,2-dithiol and boron trifluoride-diethyl ether.The derived (7R,8R,9R)-9-benzoyloxy-7,8-dihydroxy-1,4-dithiaspirodecane (15a), when treated sequentially with lead(IV) acetate and pyrrolidinium acetate, underwent an oxidative ring contraction to give (8R)-8-benzoyloxy-1,4-dithiaspironon-6-ene-6-carbaldehyde (17a). The aldehyde (17a) reacted with lithium aluminium hydride to give (8R)-8-hydroxy-6-hydroxymethyl-1,4-dithiaspironon-6-ene (18a) and with sodium cyanoborohydride to yield (8R)-8-benzoyloxy-6-hydroxymethyl-1,4-dithiaspironon-6-ene (18b).Sodium methoxide effected the transformation of the hydroxybenzoate (18b) into the diol (18a) which underwent benzylation with benzyl bromide to give the dibenzyl ether (18c).Benzoylation of the hydroxybenzoate (18b), to give the dibenzoate (18d), was achieved by the action of benzoyl chloride.Removal of the dithiolane moiety from compounds (18a-d), to give the cyclopent-2-en-1-ones (1a-d), was brought about by copper(II) chloride-copper(II) oxide. The cyclohexanone (11b) also reacted with propane-1,3-dithiol and boron trifluoride-diethyl ether to give (8R,9R,10R)-10-benzoyloxy-8,9-dihydroxy-1,5-dithiaspiroundecane (20), which underwent an oxidative ring contraction to (9R)-9-benzoyloxy-1,5-dithiaspirodec-7-ene-7-carbaldehyde (22) when treated with lead(IV) acetate followed by dibenzylamine trifluoroacetate. The outcome of the reaction of the cyclohexanone (11b) with ethane-1,2-diol depended upon the reaction conditions.In refluxing benzene and in the presence of toluene-p-sulphonic acid, 1-hydroxy-4-(2-hydroxyethoxy)benzene (24) was formed.At room temperature and in the presence of sulphuric acid, (7R,8R,9R)-9-benzyloxy-7,8-dihydroxy-1,4-dioxaspirodecane (15c) was the major product.Although the oxidative ring contraction of the last-mentioned derivative was also effected by the action of lead(IV) acetate followed by dibenzylamine trifluoroacetate, the resultant (8R)-8-benzoyloxy-1,4-dioxaspironon-6-ene-6-carbaldehyde (17c) was an unstable entity. Compounds (17a) and (22) inhibited the growth of Staphylococcus aureus at concentrations of 2 and 32 μg cm-3, respectively.
Studies related to Cyclopentanoid Natural Products. Part 1. Preparation of (4RS)- and (4R)-4-Hydroxy-2-hydroxymethylcyclopent-2-en-1-one; a Versatile Synthetic Intermediate
Elliott, John D.,Hetmanski, Michael,Stoodley, Richard J.,Palfreyman, Malcolm N.
, p. 1782 - 1789 (2007/10/02)
The racemate of 2,5-dihydro-3-hydroxymethyl-2,5-dimethoxy-2-methylfuran (11), prepared from the reaction of 3-hydroxymethyl-2-methylfuran (12b), with bromine in methanol, is converted into the racemate of 4-hydroxy-2-hydroxymethylcyclopent-2-en-1-one (9a) when heated in aqueous dioxan buffered at pH 6.3. Methyl quinate (17b), obtained by treating D-(-)-quinic acid (17a) with methanolic hydrogen chloride, reacts with ammonia in methanol to give quinamide (17c) which affords 1,1'-ON-isopropylidenequinamide (27a) in the presence of acetone containing hydrogen chloride.Benzoyl chloride in pyridine transforms compound (27a) into the 5-O-benzoate (27b) which undergoes selective hydrolysis in hot aqueous acetic acid to give 5-O-benzoyl-1,1'-ON-isopropylidenequinamide (26).Sequential treatment of compound (26) with sodium periodate in aqueous tetrahydrofuran (THF) and pyrrolidinium acetate in hot benzene affords (5R,8R)-8-benzoyloxy-2,2-dimethyl-4-oxo-3-azaspironon-6-ene-6-carbaldehyde (32).The aldehyde (32) is transformed into (5R,8R)-8-hydroxy-6-hydroxymethyl-2,2-dimethyl-1-oxa-3-azaspironon-6-en-4-one (34a) by reaction with sodium borohydride in THF followed by methanolic sodium methoxide.Hydrazinolysis of the oxazolidinone ring of the last-described compound is effected in boiling hydrazine hydrate to yield (1R,4R)-1,4-dihydroxy-2-hydroxymethylcyclopent-2-ene-1-carbohydrazide (35a).Treatment of the acid hydrazide (35a) with nitrous acid and thermolysis of the derived acid azide (35b) gives (4R)-4-hydroxy-2-hydroxymethylcyclopent-2-en-1-one (9a).
4-Hydroxy-2-hydroxymethylcyclopent-2-en-1-one: a Versatile Intermediate for the Synthesis of Cyclopentanoid Natural Products
Elliott, John D.,Hetmanski, Michael,Stoodley, Richard J.,Palfreyman, Malcolm N.
, p. 924 - 925 (2007/10/02)
The title compound has been prepared as the racemate, by way of 3-hydroxymethyl-2-methylfuran, and as the (4R)-isomer, starting with (-)-quinic acid.
