Total Syntheses of Paraconic Acids and 1,10-seco-Guaianolides via a Barbier Allylation/Translactonization Cascade of 3‑(Bromomethyl)-2(5H)‑furanone
journal contributionposted on 27.01.2021, 20:04 by Weilong Liu, Zhimei Yu, Nicolas Winssinger
A palladium-catalyzed Barbier allylation/translactonization cascade reaction was established for the rapid construction of β,γ-disubstituted α-exo-methylene-γ-butyrolactone, an important motif in sesquiterpenes. Dimethyl zinc played significant roles in both steps for the umpolung of π-allylpalladium as a nucleophile and promoting a Lewis acid-mediated translactonization. This sequence showed a broad substrate scope and was further harnessed for the synthesis of two paraconic acids as well as the first protecting-group-free total synthesis of two 1,10-seco-guaianolides.
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furanonemotifsequenceumpolungmethylene -γ-butyrolactoneguaianolideTotal SynthesesBromomethylLewis acid-mediated translactonizationDimethyl zincprotecting-group-freesubstrate scopeGuaianolidenucleophileroleBarbierAllylationconstructionsynthesispalladium-catalyzedparaconic acidsπ- allylpalladiumCascadeallylationexosesquiterpenesecocascadeParaconic Acidsdisubstitutedα-