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A Convergent Total Synthesis of (+)-Ineleganolide
Benjamin M Gross1, Seo-Jung Han1,2, Scott C Virgil1
1The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, California Institute of Technology, MC-101-20, Pasadena, California 91125, United States.
Abstract:
We report the total synthesis of the furanobutenolide-derived diterpenoid (+)-ineleganolide. The synthetic approach relies on a convergent strategy based on the coupling of two enantioenriched fragments, which are derived from (-)-linalool and (+)-norcarvone, respectively. A high-yielding, one-step Michael addition and aldol cascade furnishes a pentacyclic framework as a single diastereomer, thereby overcoming previous challenges in controlling stereochemistry. The endgame features an O2-facilitated C-H oxidation and a samarium diiodide-induced semipinacol rearrangement to furnish the highly rigid central seven-membered ring.
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