The Palladium-Catalyzed Enyne Cycloisomerization Reaction in a General Approach to the Asymmetric Syntheses of the Picrotoxane Sesquiterpenes. Part I. First-Generation Total Synthesis of Corianin and

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• 作者：Barry M. Trost ; Curt D. Haffner ; David J. Jebaratnam ; Michael J. Krische ; and Andrew P. Thomas
• 刊名：Journal of the American Chemical Society
• 出版年：1999
• 出版时间：July 7, 1999
• 年：1999
• 卷：121
• 期：26
• 页码：6183 - 6192
• 全文大小：350K
• 年卷期：v.121,no.26(July 7, 1999)
• ISSN：1520-5126

文摘

The palladium-catalyzed enyne cycloisomerization is used as a key ring-forming process for theobtention of the cis-fused hydrindane carbon skeleton characteristic of the picrotoxanes sesquiterpenes. Theenyne cycloisomerization product is suitably functionalized so that each carbon of the hydrindane core can bemodified to permit access to many members of the picrotoxane family, not only to picrotoxinin itself. Part Iof this report describes our first-generation approach to the picrotoxane sesquiterpenes as illustrated by theasymmetric synthesis of corianin and the asymmetric formal syntheses of picrotoxinin and picrotin. A newcatalyst system to effect the cycloisomerization emerged from this study. Subsequent work proved the generalityof this catalyst system.