A convergent route toward the synthesis of leiodolide A () is described. Our studies explored reactions of the indium chloride-induced transmetalation of allylic stannane for nucleophilic addition with nonracemic aldehyde . The stereoselective formation of the all- stereotriad was rationalized by an isomerization to produce the -allylindium reagent for subsequent -Felkin addition. The inversion of C stereochemistry led to an effective π-allyl Stille cross coupling utilizing -alkenylstannane . The Horner-Wadsworth-Emmons reaction provides macrolactone which exhibits discrepancies as compared with reported NMR data for the purported leiodolide A.
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Synthesis of Leiodolide A Macrolactone.
Org Lett
March 2025
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
A convergent route toward the synthesis of leiodolide A () is described. Our studies explored reactions of the indium chloride-induced transmetalation of allylic stannane for nucleophilic addition with nonracemic aldehyde . The stereoselective formation of the all- stereotriad was rationalized by an isomerization to produce the -allylindium reagent for subsequent -Felkin addition.
View Article and Find Full Text PDFStudies Toward the Synthesis of Leiodolide A.
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March 2025
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
Studies have described a highly convergent plan toward the synthesis of leiodolide A (), a potent cytotoxic sponge metabolite. The enantiocontrolled preparation of aldehyde is achieved with the application of several advances in methodology for the synthesis of substituted 1,3-oxazoles. Efforts have examined the halogen dance reaction, the selectivity of Stille cross coupling reactions of 4-bromo-1,3-oxazoles, and nucleophilic displacement of the 2-phenylsulfonyl substituent with organolithium reagents as preparatively useful reactions.
View Article and Find Full Text PDFThe leiodolide B puzzle.
Angew Chem Int Ed Engl
January 2011
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
Catalytic enantioselective alkylation of substituted dioxanone enol ethers: ready access to Calpha-tetrasubstituted hydroxyketones, acids, and esters.
Angew Chem Int Ed Engl
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Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Boulevard MC 164-30, Pasadena, CA 91125, USA.
The catalytic enantioselective formation of tetrasubstituted α-alkoxycarbonyl compounds is an ongoing challenge to synthetic chemists.[1] Fully-substituted α-hydroxyesters and acids comprise essential components of, and building blocks for, many bioactive natural products. These include quinic acid (), cytotoxic leiodolide A (),[2] and the anti-cancer agents in the harringtonine series (–), whose activities depend dramatically on the presence and composition of an α-hydroxyester side-chain.
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