Structure and Synthesis of a Derivative of Prostaglandin E1. Prostaglandins and Related Factors 16.

Samuelsson, Bengt; Ställberg, Gunnel; Arro, Leonida; Kvande, P. C.; Meisingseth, E.

doi:10.3891/acta.chem.scand.17-0810

Cited by 34 publications

(6 citation statements)

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“…8 : colorless oil; IR (CHCl 3 ) 2930, 2850, 1710, 1600 cm -1 ; 1 H NMR (CDCl 3 ) δ 3.88 (s, 2H), 2.65 (t, J = 7.0 Hz, 2H), 1.61−1.54 (m, 2H), 1.32−1.24 (m, 10H), 0.88 (t, J = 6.0 Hz, 3H); 13 C NMR (CDCl 3 ) δ 202.3 (s), 39.9 (t), 34.3 (t), 31.8 (t), 29.3 (t), 29.10 (t), 29.05 (t), 23.9 (t), 22.6 (t), 14.1 (q); MS m / z (relative intensity) 236 (0.4), 234 (0.4, M + ), 155 (7), 141 (100), 85 (48), 83 (76), 57 (39); HRMS calcd for C 10 H 19 OBr (M + ) 234.0619, found 234.0620. Anal.…”

Section: Methodsmentioning

confidence: 99%

Generation and Reaction of Monocarbonyliodonium Ylides: Ester Exchange of (Z)-(β-Acetoxyvinyl)iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones

1997

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Reported here for the first time are the generation of monocarbonyliodonium ylides and their alkylidene-transfer reactions to aldehydes yielding α,β-epoxy ketones. Exposure of (Z)-(2-acetoxy-1-decenyl)iodonium bromide, prepared stereoselectively by sodium acetate-catalyzed Michael addition of acetic acid to (1-decynyl)(phenyl)iodonium salt, to EtOLi in THF at −78 °C results in ester exchange to generate the monocarbonyliodonium ylide with the liberation of ethyl acetate. 1H NMR measurements indicate that the ylide is stable up to −30 °C in THF-d 8 but gradually decomposes at −20 °C to 1-bromo-2-decanone. The monocarbonyliodonium ylide acts as an alkylidene-transfer agent to carbonyl compounds, and the reaction with aldehydes in THF−DMSO at −30 °C gives α,β-epoxy ketones with E-isomers as a major product. With an α,β-unsaturated aldehyde, selective 1,2-addition to the carbonyl group was observed. The relative rates of the alkylidene-transfer reaction of this ylide for a series of ring-substituted benzaldehydes were measured. A Hammett correlation plot with the σ constants of substituents afforded the reaction constant ρ = 2.95 (r = 1.00), which indicates that the monocarbonyliodonium ylide is moderately nucleophilic in nature.

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Section: Methodsmentioning

confidence: 99%

Generation and Reaction of Monocarbonyliodonium Ylides: Ester Exchange of (Z)-(β-Acetoxyvinyl)iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones

1997

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“…An acid with the carbon skeleton of PGEI and containing the keto group was also prepared synthetically and found to be identical with a derivative of PGEI in which the hydroxyl groups had been eliminated and the resulting double bonds reduced (14). This was also confirmed by the nuclear magnetic resonance data demonstrating absence of olefinic protons in this derivative.…”

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confidence: 68%

Prostaglandins

Bergström¹,

Samuelsson²

1965

Annu. Rev. Biochem.

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Isolation and structure determination,-In 1933-1934 Goldblatt (1, 2) and von Euler (3) independently demonstrated that extracts of human seminal plasma and of the vesicular gland of sheep produce a fall in blood pressure and stimulate a variety of smooth muscle organs. The active material was named prostaglandin by von Euler, who also showed that it was lipid soluble and had acidic properties (4-7).In 1957 Bergstrom & Sjovall isolated two crystalline compounds from the vesicular gland of sheep (8-10). One of these compounds, PGF1cx, possessed smooth muscle stimulating activity and the other, PGE1, also showed strong vasodepressor activity. Later, two additional compounds called PGE2 and PGE 3 were isolated in pure form from the same source by Bergstrom et al. (11). The biological effects of these compounds were similar to those of PGE1•The structure of PGE1 was reported in 1962 by Bergstrom et ai. (12, 13), The salient reactions upon which this structure was based will be briefly discussed. Various physical methods indicated that PGE 1 was a C20 car boxylic acid (C2oH3406) having two hydroxyl groups, one keto group in a five membered ring and one trans double bond. Alkali transformed PGE1 into a derivative with X max at 278 mJ.!. The fragments formed on oxidative ozo nolysis of the acetylated methyl ester of this derivative were separated by gas-liquid chromatography and identified by mass spectrometry. In all, 19 of the 20 carbon atoms could be accounted for as the monomethyl ester of suberic acid, succinic acid, and a-acetoxy-heptanoic acid. Another derivative, prepared by treatment of hydrogenated PGE1 with alkali, was also degraded after treatment with diazomethane and acetylation. Two products, viz., the monomethyl ester of suberic acid and 7-acetoxy-4-ketododecanoic acid, were formed. The structure of the degraded derivative was supported by its ultra violet absorption (X max 237 mJ.!) which was in agreement with the values 1 The survey of the literature pertaining to this review was concluded in September 1964.I The following abbreviations are used: PGE1 (Prostaglandin El-lla,15-dihy droxy-9-keto-prost-13-enoic acid); PGE2 (Prostaglandin E:r-lla,15-dihydroxy-9keto-prosta-5,13-dienoic acid); PGE3 (Prostaglandin E:r-lla-15-dihydroxy-9-keto prosta-S,13,17-trienoic acid); PGF'a (earlier PGF,_,) (Prostaglandin F",-9a,l1a,15trihydroxy-prost-13-enoic acid); PGF'Ii (earlier PGF2_1) (Prostaglandin FIjS-9!3,l1a, IS-trihydroxydroxy-prost-13-enoic acid); PGF2a (earlier PGF'_2) (Prostaglandin F2",-9a,l1a,lS-trihydroxy-prosta-5,13-dienoic acid); PGF21i (earlier PGF2_.) (Pro staglandin F�9,8,l1a,lS-trihydroxy-prosta-5,13-dienoic acid); PGFsa (earlier PGF1_S) (Prostaglandin Fsa-9a,l1a,lS-trihydroxy-prosta-S,13,17-trienoic acid); PGF B!i (earlier PGF2_S) (Prostaglandin F ap-9!3, lla,lS-trihydroxy-prosta-S, 13, 17-tri enoic acid). 101 Annu. Rev. Biochem. 1965.34:101-108. Downloaded from www.annualreviews.org Access provided by Northwestern University -Evanston Campus on 02/07/15. For personal use only. Quick links to online...

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“…Data for 1-Bromo-5-phenyl-2-pentanone (15b): colorless oil; IR (neat) 1715, 701 cm -1 ; 1 H NMR (CDCl3) δ 7.35-7.13 (m, 10H), 3.85 (s, 2H), 2.66 (t, J ) 7.4 Hz, 2H), 2.65 (t, J ) 7.4 Hz, 2H), 1.96 (quint, J ) 7.4 Hz, 2H); MS m/z (relative intensity) 240 (M + , 3), 161 (10), 147 (6), 104 (100), 91 (37).…”

Section: Methodsmentioning

confidence: 99%

A New Route for Generation of α-λ³-Iodanyl Ketones via Ester Exchange of (Z)-(β-Acetoxyvinyl)-λ³-iodanes: Their Nucleophilic Substitutions with Halides and Sulfur and Phosphorus Nucleophiles

2002

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An efficient method for generation of alpha-lambda3-iodanyl ketones from (Z)-(2-acetoxyvinyl)(phenyl)-lambda3-iodanes was developed. The method involves ester exchange of (Z)-2-acetoxyvinyl-lambda3-iodanes with methanol in the presence of triethylamine. alpha-lambda3-Iodanyl ketones react with a variety of nucleophiles such as halides, thiols, phosphines, phosphinic acids, and phosphates, under the conditions which produce alpha-functionalized carbonyl compounds probably via an S(N)2 pathway.

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Structure and Synthesis of a Derivative of Prostaglandin E1. Prostaglandins and Related Factors 16.

Cited by 34 publications

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Generation and Reaction of Monocarbonyliodonium Ylides: Ester Exchange of (Z)-(β-Acetoxyvinyl)iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones

Generation and Reaction of Monocarbonyliodonium Ylides: Ester Exchange of (Z)-(β-Acetoxyvinyl)iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones

Prostaglandins

A New Route for Generation of α-λ³-Iodanyl Ketones via Ester Exchange of (Z)-(β-Acetoxyvinyl)-λ³-iodanes: Their Nucleophilic Substitutions with Halides and Sulfur and Phosphorus Nucleophiles

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Structure and Synthesis of a Derivative of Prostaglandin E1. Prostaglandins and Related Factors 16.

Cited by 34 publications

References 0 publications

Generation and Reaction of Monocarbonyliodonium Ylides: Ester Exchange of (Z)-(β-Acetoxyvinyl)iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones

Generation and Reaction of Monocarbonyliodonium Ylides: Ester Exchange of (Z)-(β-Acetoxyvinyl)iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones

Prostaglandins

A New Route for Generation of α-λ3-Iodanyl Ketones via Ester Exchange of (Z)-(β-Acetoxyvinyl)-λ3-iodanes: Their Nucleophilic Substitutions with Halides and Sulfur and Phosphorus Nucleophiles

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A New Route for Generation of α-λ³-Iodanyl Ketones via Ester Exchange of (Z)-(β-Acetoxyvinyl)-λ³-iodanes: Their Nucleophilic Substitutions with Halides and Sulfur and Phosphorus Nucleophiles