Highly Enantio- and Diastereoselective One-Pot Synthesis of Acyclic Epoxy Alcohols and Allylic Epoxy Alcohols

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• 作者：Ann Rowley Kelly ; Alice E. Lurain ; and Patrick J. Walsh
• 刊名：Journal of the American Chemical Society
• 出版年：2005
• 出版时间：October 26, 2005
• 年：2005
• 卷：127
• 期：42
• 页码：14668 - 14674
• 全文大小：153K
• 年卷期：v.127,no.42(October 26, 2005)
• ISSN：1520-5126

文摘

In this report, we outline a highly enantio- and diastereoselective one-pot method for the efficientsynthesis of synthetically useful acyclic epoxy alcohols and allylic epoxy alcohols. Our method takesadvantage of a highly enantioselective C-C bond-forming reaction to set the initial chirality. The resultingallylic zinc alkoxide intermediate is then epoxidized in situ using either dioxygen or TBHP in the presenceof a titanium tetraalkoxide. Epoxy alcohols with up to three contiguous stereocenters are formed in one potwith excellent enantio- and diastereoselectivity. In cases where the zinc alkoxide intermediates containtwo different allylic olefins, the more electron-rich double bond is chemoselectively epoxidized to afford anallylic epoxy alcohol. This method represents a highly efficient, stereoselective, and chemoselective approachto the synthesis of a wide range of useful epoxy alcohol and allylic epoxy alcohol products that werepreviously difficult to access.