Theoretical Studies on Synthetic and Biosynthetic Oxidopyrylium-Alkene Cycloadditions: Pericyclic Pathways to Intricarene

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• 作者：Selina C. Wang ; Dean J. Tantillo
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：February 15, 2008
• 年：2008
• 卷：73
• 期：4
• 页码：1516 - 1523
• 全文大小：396K
• 年卷期：v.73,no.4(February 15, 2008)
• ISSN：1520-6904

文摘

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Herein we describe quantum chemical calculations (B3LYP) on the intramolecular oxidopyrylium-alkene cycloadditions used in two recently reported total syntheses of (+)-intricarene, and possibly alsooccurring during its biosynthesis. Using theory, we address (1) the necessity of enzyme intervention ifthis reaction occurs in Nature and (2) the effects of substituents attached to the oxidopyrylium and alkenegroups on the activation barriers for cycloaddition.