Oxidation products of arachidonic acid II. The synthesis of methyl 8R,9S,11R-trihydroxy-5Z,12E,14Z-eicosatrienoate

Just, George; Luthe, C. E.

doi:10.1139/v80-284

Cited by 32 publications

(8 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…5 Methanesulfonyl chloride (4 g, 35 mmol) was added to a solution g, 95% Sodium iodide (2.2 g, 33.4 mmol) and zinc (5.0 g, 33.4 mmol) were added to a solution of dimesylate 6 (2.4 g, 6.68 mmol) in dimethoxyethane (50 mL). The mixture was allowed to reflux for 2h, after which the solution was filtered, hexane was added (100 mL), and the hexane solution was washed once with water (50 mL) and once with an aqueous solution of saturated sodium thiosulfate.…”

Section: ~mentioning

confidence: 99%

Synthesis and resolution of R(−)-5-hexyn-3-ol

Roy¹,

Deslongchamps²

1985

Can. J. Chem.

View full text Add to dashboard Cite

. J . Chem. 63, 65 1 (1 985).The resolution of (*)-5-hexyn-3-01 (1) was effected by high performance chromatography of its 0-methyl mandelic esters 3 and 4. The absolute configuration of (-) and (+)-5-hexyn-3-01 were determined by comparison with an authentic sample prepared from D(+)-glucose. BERNARD L. ROY et PIERRE DESLONGCHAMPS. Can. J . Chem. 63, 651 (1985). La rCsolution du (?)-hexyne-5 01-3 (1) fut rtalisCe grice ii la chromatographie ii haute performance de ses esters 0-methyl mandtlique 3 et 4. La configuration absolue du (-) et (+)-hexyne-5 01-3 fut determinee par comparaison avec un echantillon prepare ii partir du D ( + ) -~~u c o s~.As part of our work on the total synthesis of erythromycin A,' the R enantiorner of 5-hexyn-3-01 ( 1 R ) was required as starting material. We have obtained this compound by resolution and wish to report this work.The racemic form of 1 (Scheme I), which is readily available from the condensation of propargyl magnesium bromide on propionaldehyde (3), was transformed into the corresponding diasteroisomeric 0-methyl mandelic esters 3 and 4 by reaction with optically active acid chloride 2 (4). The separation of diastereoisomers 3 and 4 was carried out by high performance chromatography using toluene -ethyl acetate (99.5 : 0.5) as the solvent. After separation, the more polar compound had an [a]: +86" ( c I . I, CHCI,) and the less polar had an [a]: +2S0 (C 1.9, CHCI,).Referring to Mosher's work (4) on the anisotropic effect of the phenyl ring on proton chemical shifts, we were able to predict that the more polar diastereoisomer would correspond to 3 and the less polar to 4, having respectively the SR and the SS absolute configuration. This assignment is based on the fact that (a) the protons at CI and C2 in 3 (Table I ) absorb at a higher field than those in 4, and (b) the protons at C4 and C6 in 3 absorb at a lower field than those in 4.Hydrolysis of the more polar diastereoisomer 3 gave an alcohol ([a]: -4O (c 1. I, CHCI,)) which must therefore have the R absolute configuration, whereas the less polar diastereoisomer 4 yielded an alcohol ([a]: +4" ( c 2.1, CHCI,)) having the S configuration.This configurational assignment based on Mosher's work (4), was rigorously established by preparing a sample of alcohol 1R starting from D-glucose using the method described in Scheme 2. The known compound 5 (5,6) was prepared in four steps from D-glucose. The alcohol 1R obtained from compound 11 was levorotatory ([a];?: -4" (c I. I, CHCI,)), so our original assignment was correct. The alcohol 1 s can also be transformed into the benzoate 12 of alcohol 1R using the Mitsunobu inversion procedure (7). The benzoate 12 obtained had a rotation ([a]: +2S0 ( c 1.6, CHCI,)) essentially identical to that of an authentic sample of 12 ([af +29" (c 1.2, CHCI,)) prepared by benzoylation of alcohol I R . ExperimentalThe infrared (ir) spectra were taken on a Perkin-Elmer 681 spec- 'NSERCC and FCAC predoctoral fellowships, 1980-1984 trophotometer. Proton nmr spectra were recorded on a Bruker WP-60 o...

show abstract

Section: ~mentioning

confidence: 99%

Synthesis and resolution of R(−)-5-hexyn-3-ol

Roy¹,

Deslongchamps²

1985

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…1, 3). In this paper, we wish to describe some model studies on this attachment and the synthesis of a derivative of type 1 having an acetylenic bond at A13, which strongly supports the structure assigned to 1.…”

mentioning

confidence: 68%

Oxidation products of arachidonic acid. IV. Model studies on the attachaient of the C(13)—C(20) side-chain in the synthesis of tetrahydrofurans and pyrans 1,2, and 3

Just¹,

Crosilla²

1980

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

GEORGE JUST and DANILO CROSILLA. Can. J. Chem. 58, 2349Chem. 58, (1980 The synthesis of methyl 15-hydroxy-8(R)-methoxy-11(R)-p-nitrobenzoyloxy-9(S),12(R)-oxy-eicosa-13-ynoate, an arachidonic acid metabolite derivative, is described. As well, methods for the attachment of the C ( 1 3 j C ( 2 0 ) prostaglandin side-chain to furanosides were studied and the results are described. The reduction of the C-15 keto group on a model compound was performed and was found to have the same behavior as in the prostaglandins.A partial structure proof of Pace-Asciak's compound, 9,12-oxy-8,11,15-trihydroxy-13-enoic acid is given.GEORGE JUST et DANILO CROSILLA. Can. J. Chem. 58,2349Chem. 58, (1980. On decrit la synthkse de I'hydroxy-15 methoxy-8(R) p-nitrobenzoyloxy-ll(R) oxy-9(S), 12(R) eicosyne-13 oate de mtthyle, un derive metabolique de I'acide arachidonique. On a egalement etudie les methodes de fixation des carbones en position 13 i 20 de la chaine laterale de la prostaglandine aux furannosides et on decrit les resultats. On a realist la reduction du groupe cetonique en position 15 sur un compose type et on a trouve qu'il se comporte comme celui des prostaglandines. On donne une preuve partielle de structure du compose de Pace-Asciak, I'acide oxy-9,12 trihydroxy-8,11,15 kne-13 oique.[Traduit par le journal]In connection with the synthesis of oxidation products of arachidonic acid of type 1, 2, and 3, isolated by Pace-Asciak and Wolfe (1) and Axelrod and co-workers (2), we had to work out procedures for attaching the C(13)-C (20) side-chain to furanose derivatives (for rationale of the choice of stereochemistry of the model compounds, see refs. 1,3). In this paper, we wish to describe some model studies on this attachment and the synthesis of a derivative of type 1 having an acetylenic bond at A13, which strongly supports the structure assigned to 1.As a model, we used 1,2-0-isopropylidene-3,5,6-tri-0-methyl-a-D-glucofuranose (5); which is easily obtained by methylation (4) of the commercially available glucofuranose 4. Hydrolysis of 5 with hydrochloric acid, followed by acetylation with p-nitrobenzoyl chloride in pyridine (5) gave 7 as a mixture of anomers. Treatment with hydrogen bromide in benzene at 0°C (6) transformed 7 to bromides 8, which, when submitted to the action of mercuric cyanide in nitromethane (6), gave the Pcyanide 9 as one isomer only, as established by nmr which showed the C(l) hydrogen as a broad singlet (J,,, 2 0-1) indicating a HI,,-dihedral angle of approximately 90°C. Alkaline hydrolysis gave the cyano alcohol

show abstract

“…cially available d-diacetone glucose (d-104), which was converted in six steps into homopropargylic alcohol 105. [213] The alcohol function in 105 was converted into the iodide in a Finkelstein reaction, followed by ring opening of the modified furanose to the dithioacetal. Protection of the remaining hydroxy group as a TES ether delivered the C1-C12 subunit 106 in good yield.…”

Section: Cyclopentane-containing Pufa Metabolites-isopsmentioning

confidence: 99%

Beyond Prostaglandins—Chemistry and Biology of Cyclic Oxygenated Metabolites Formed by Free‐Radical Pathways from Polyunsaturated Fatty Acids

2008

View full text Add to dashboard Cite

Polyunsaturated fatty acids (PUFAs) are important constituents in all organisms. They fulfil many functions, ranging from modulating the structure of membranes to acting as precursors of physiologically important molecules, such as the prostaglandins, which for a long time were the most prominent cyclic PUFA metabolites. However, since the beginning of the 1990s a large variety of cyclic metabolites have been discovered that form under autoxidative conditions in vivo to a much larger extent than do prostaglandins. These compounds--isoprostanes, neuroprostanes, phytoprostanes, and isofurans--proved subsequently to be ubiquitous in nature. They display a wide range of biological activities, and isoprostanes have become the currently most reliable indicators of oxidative stress in humans. In a relatively short time, the structural variety, properties, and applications of the autoxidatively formed cyclic PUFA derivatives have been uncovered.

show abstract

Oxidation products of arachidonic acid II. The synthesis of methyl 8R,9S,11R-trihydroxy-5Z,12E,14Z-eicosatrienoate

Cited by 32 publications

References 7 publications

Synthesis and resolution of R(−)-5-hexyn-3-ol

Synthesis and resolution of R(−)-5-hexyn-3-ol

Oxidation products of arachidonic acid. IV. Model studies on the attachaient of the C(13)—C(20) side-chain in the synthesis of tetrahydrofurans and pyrans 1,2, and 3

Beyond Prostaglandins—Chemistry and Biology of Cyclic Oxygenated Metabolites Formed by Free‐Radical Pathways from Polyunsaturated Fatty Acids

Contact Info

Product

Resources

About