Facile synthesis of methanesulfonate esters

Crossland, R. K.; Servis, Kenneth L.

doi:10.1021/jo00834a087

Cited by 419 publications

(231 citation statements)

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“…8 is ref. carried out using mesyl chloride (3 eq) and triethylamine (3 eq) in methylene chloride (40 ml/g of VII) at -20°for 1 hr using the standard method (13 (14). Contraction of Rabbit Aorta Strips.…”

mentioning

confidence: 99%

Synthesis and biological properties of a 9,11-azo-prostanoid: highly active biochemical mimic of prostaglandin endoperoxides.

Corey¹,

Nicolaou²,

Machida³

et al. 1975

Proc. Natl. Acad. Sci. U.S.A.

116

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The 9,11-azo-prostanoid III [(5Z, 9a, Ila, 13E, has been obtained by synthesis and tested for biological activity in systems which are responsive to the prostaglandin endoperoxides PGH2 (I) and PGG2 (II). The azo analog III is a powerful mimic of these endoperoxides with reference to platelet aggregation and release of serotonin when added to human platelet-rich plasma. The analog III is substantially more active (about 7 fold) than PGG2 in stimulating muscle contraction in the isolated rabbit aorta strip. The very great stability of III relative to PGH2 and PGG2 and its potency as a mimic of these important substances suggest that this azo analog will be of considerable value in future studies of the prostaglandin endoperoxides. The two prostaglandin (PG) endoperoxides, PGH2 (I, Fig. 1) and PGG2 (II), derived in vio from arachidonic acid, are very potent in inducing rapid and irreversible aggregation of human platelets through release of ADP and serotonin (1-8). The endoperoxides are rapidly metabolized to a hemiacetal derivative 8-(1-hydroxy-3-oxopropyl)-9, 12L-dihydroxy-5,10-heptadecadienoic acid (PHD) in platelets, and this metabolite is released in large amounts during aggregation induced by various agents (4, 5). A physiological role of the endoperoxide system in human platelets has been established through studies demonstrating that a hemostatic defect involving an abnormal platelet release mechanism was due to deficiency of the cyclo-oxygenase responsible for endoperoxide synthesis (3). The endoperoxides are also potent stimulants of vascular (rabbit aorta and umbilical artery) and air-way smooth muscle (6).The endoperoxides PGH2 and PGG2 are intrinsically highly unstable substances (half-life, t1/2, about 5 min in aqueous solution at 370 and pH 7.4). Further, they are transformed with great rapidity enzymically [e.g., t1/2 about 10 sec in platelet-rich plasma (PRP)]. Because of the extraordinary lability of these endoperoxides and the consequent difficulties and limitations in experimental use, the design and synthesis of a stable and active analog was deemed important. The most interesting analog for initial study appeared to be the azo compound represented by formula III in Fig. 1. It was anticipated that this substance would possess very nearly the same molecular geometry as PGH2 (I), but would be indefinitely stable at pH 7 and 370. Although there was no assurance a priori that III would behave as a close mimic of PGH2 (or PGG2) rather than as an antagonist, the experimental resolution of this question itself seemed worthwhile as a step toward a better understanding of the biochemical mode of action of PGH2.MATERIALS AND METHODS The preparation of the endoperoxides PGG2 and PGH2 has been described previously (2). Blood from healthy donors, who had not taken any drugs for at least 1 week, was collected from the antecubital vein with 0.13 volume of 0.1 M trisodium citrate. After centrifugation at 200 X g for 15 min at room temperature, PRP was removed. Calcium chloride (10 ,ul 0.25 M solutio...

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mentioning

confidence: 99%

Synthesis and biological properties of a 9,11-azo-prostanoid: highly active biochemical mimic of prostaglandin endoperoxides.

Corey¹,

Nicolaou²,

Machida³

et al. 1975

Proc. Natl. Acad. Sci. U.S.A.

116

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“…It is important to mention that cupric chloride was used as catalyst because there are several reports which indicate that copper(I) reagent has been found tobe an efficient catalyst for an enantioselective one-pot threecomponent synthesisbetween aldehydes, amines and alkynes [15][16] .The results indicate that 1 H NMR spectrum of 6showed several signals at 0.91 ppm corresponding to methyl presents in the alkyne fragment; at 1.42-2.32 ppm for methylenes bound to alkyne group; at 2.88-3.14 ppm for methylenes bound to amino groups; at 4.70 ppm for both amino and hydroxyl groups; at 5.02 ppm for the methylene bound to both amino and phenyl groups. Finally, other signals at6.61-7.75 ppm for protons involved in phenyl groups were found.…”

Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Three Naphtol Derivatives using the Three Component System

Figueroa‐Valverde

Díaz-Cedillo²,

Elodia

et al. 2012

Orientjchem.

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“…Small scale Sodium metal (0.1233 g, 5.3 mmol) was reacted with 2-propanol (20 mL). Phenylmethanethiol (0.7 mL, 5.6 mmol) and the mesylate 4 (1.000 g, 5.6 mmol) (19) were added and the reaction mixture refluxed for 4 days. A standard extraction procedure furnished crude product.…”

Section: Reaction Of P-nitrophenyl Methanesulfonate With Phenoxide Ionsmentioning

confidence: 99%

“…2,2,2-Trifluoroethyl rnethanesulfonate (4.9968 g, 28.0 mmol) (19) was added and the resultant mixture refluxed for 0.5 h. Acidification and extraction afforded a residue that was chromatographed on silica gel (400 g) employing chloroform elution (100-mL fractions). Fraction 12 was concentrated, affording a mixture of dibenzyl ether (0.056 g, 0.2 mmol) and benzyl trifluoroethyl ether (0.087 g, 0.4 mmol).…”

Section: Preparation Of Dibenzyl Ethermentioning

confidence: 99%

Chemoselective reaction of a sulfonate ester with methoxide ions in preference to benzyl mercaptide anions

Langler¹,

Morrison²

1987

Can. J. Chem.

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Facile synthesis of methanesulfonate esters

Cited by 419 publications

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Synthesis and biological properties of a 9,11-azo-prostanoid: highly active biochemical mimic of prostaglandin endoperoxides.

Synthesis and biological properties of a 9,11-azo-prostanoid: highly active biochemical mimic of prostaglandin endoperoxides.

Design and Synthesis of Three Naphtol Derivatives using the Three Component System

Chemoselective reaction of a sulfonate ester with methoxide ions in preference to benzyl mercaptide anions

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