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Asymmetric Total Synthesis of (-)-Crotonine G and (-)-Crotonolide D
Hao Yu1, Yutaro Hatano1, Peng-Jui Chen1
1The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Abstract:
The first enantioselective total syntheses of crotonine G and crotonolide D are disclosed. The synthetic approach employs a SmI2 mediated ketyl radical cyclization to form the highly congested quaternary carbon at the center of these complex molecules. Following the furan introduction, the core structure of the natural product is constructed via oxidative olefin cleavage to install the unusual C-19 and C-20 oxidation. Finally, palladium-catalyzed carbonylation, furan oxidation and acid mediated condensation/epimerization complete the synthesis.
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