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Total Syntheses of Allelopathic 4-Oxyprotoilludanes, Melleolides, and Echinocidins
Kazuma Shimoda1, Yousuke Yamaoka1, Dongeun Yoo1
1Graduate School of Pharmaceutical Sciences , Kyoto University , Yoshida, Sakyo-ku, Kyoto 606-8501 , Japan.
Abstract:
Stereocontrolled total syntheses of allelopathic 4-oxyprotoilludane sesquiterpenes, melleolide, melleolide F, and echinocidins B and D were achieved. The curved 5/6/4 tricyclic system with an angular hydroxy group was built via three key transformations: (1) Me3Al-catalyzed [2 + 2] cycloaddition of a ketene silyl acetal with a propiolate, (2) reductive ring-opening of a cyclic hemiketal, and (3) the intramolecular Morita-Baylis-Hillman reaction. This synthetic route represents a new and reliable strategy to obtain protoilludanes with several oxy-functional groups.
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