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A coordinatively unsaturated ruthenium complex catalyzed the formation of a carbon-carbon bond between two judiciously chosen alkene and alkyne partners in good yield, and in a chemo- and regioselective fashion, in spite of the significant degree of unsaturation of the substrates. The resulting 1,4-diene forms the backbone of the cytotoxic marine natural product amphidinolide P. The alkene partner was rapidly assembled from (R)-glycidyl tosylate, which served as a linchpin in a one-flask, sequential three-components coupling process using vinyllithium and a vinyl cyanocuprate. The synthesis of the alkyne partner made use of an unusual anti-selective addition under chelation control conditions of an allyltin reagent derived from tiglic acid. In addition, a remarkably E-selective E2 process using the azodicarboxylate-triphenylphosphine system is featured. Also featured is the first example of the use of a β-lactone as a thermodynamic spring to effect macrolactonization. The oxetanone ring was thus used as a productive protecting group that increased the overall efficiency of this total synthesis. This work was also an opportunity to further probe the scope of the ruthenium-catalyzed alkene-alkyne coupling, in particular using enynes, and studies using various functionalized substrates are described.

-Glycidyl Tosylate: Synonym: p-Toluenesulfonic Acid (2R)-(-)-Glycidyl Ester: General Information.
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Our third approach is depicted in , with commercially available (R)-glycidyl tosylate (34) and (R)-hydroxyisobutyric acid methyl ester (Roche ester, 48) envisioned as starting material. We planned to prepare vinyl bromide 47 from alcohol 48. We envisioned that epoxide 34 would serve as a linchpin to connect metallated 47 and vinyl lithium, thus exploiting the difference of reactivity between the two electrophilic sites of 34. Alcohol 46 thus obtained would then be converted in five steps to dioxenone 4, via 45 and 44.


(2S)-(+)-Glycidyl tosylate CAS#: 70987-78-9

(2S)-(+)-GLYCIDYL TOSYLATE: Synthesis (TRIFLUOROMETHYL)-TRIMETHYLSILANE: Synthesis ..
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Our third approach is depicted in , with commercially available (R)-glycidyl tosylate (34) and (R)-hydroxyisobutyric acid methyl ester (Roche ester, 48) envisioned as starting material. We planned to prepare vinyl bromide 47 from alcohol 48. We envisioned that epoxide 34 would serve as a linchpin to connect metallated 47 and vinyl lithium, thus exploiting the difference of reactivity between the two electrophilic sites of 34. Alcohol 46 thus obtained would then be converted in five steps to dioxenone 4, via 45 and 44.


Synthesis of GAP and PAMMO Homopolymers from …

()-Glycidyl tosylate is reduced to ()-propane-1,2-diol 1-monotosylate with and a catalytic amount of , as shown in eq 4.One of the few reported additions of a carbon nucleophile to underivatized glycidol is that of diethyl sodiomalonate.

Isotactic poly(glycidyl nitrate) and synthesis ..

The first is a very thorough review of the properties and reactions of glycidol written by Kleemann and Wagner. In the second, the use of glycidol and glycidol derivatives as synthons, with a strong emphasis on nonracemic glycidol, is the subject of a superb review by Hanson.Glycidol is a versatile three-carbon synthetic building block and its value is greatly expanded through derivatization of the hydroxyl group.

glycidyl tosylate or its enantiomer ..

In addition to the examples included below, many others may be found in Hanson's review.Single carbons can be added as cyanide using ,, diethylaluminum cyanide (eq 6),, or or as methyl groups using an organocuprate (eq 7). A single carbon may be added with dithiane salts and an example of addition of a substituted to -benzyl glycidol is shown in eq 8.Other alkyl groups, alkenyl groups (eq 9), and aryl groups have been added to glycidol via organometallic reagents.