Platinum-Catalyzed Substitution of Allylic Fluorides

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• 作者：Elena Benedetto ; Massaba Keita ; Matthew Tredwell ; Charlotte Hollingworth ; John M. Brown ; V茅ronique Gouverneur
• 刊名：Organometallics
• 出版年：2012
• 出版时间：February 27, 2012
• 年：2012
• 卷：31
• 期：4
• 页码：1408-1416
• 全文大小：429K
• 年卷期：v.31,no.4(February 27, 2012)
• ISSN：1520-6041

文摘

Allyl fluorides are reactive toward Pt-catalyzed alkylation with malonate and likewise toward N- and O-nucleophiles under mild conditions. The reactivity of fluoride as a leaving group equals or exceeds that of the esters and carbonates commonly employed in allylic alkylation. The order of leaving-group ability with Pt catalysts was found to be F 鈮?OCO₂Me OBz 鈮?OAc. This discouraged the application of platinum catalysts for the reverse reaction, fluorination of allylic substrates. Fluoride displacement involves predominant or complete retention of configuration in all the observed cases, and this was confirmed as a general feature of Pt catalysis, the stereochemical integrity being as high or higher as in Pd catalysis for the examples chosen.