Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines

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• 作者：Christopher W. Bond ; Alexander J. Cresswell ; Stephen G. Davies ; Ai M. Fletcher ; Wataru Kurosawa ; James A. Lee ; Paul M. Roberts ; Angela J. Russell ; Andrew D. Smith ; James E. Thomson
• 刊名：Journal of Organic Chemistry
• 出版年：2009
• 出版时间：September 4, 2009
• 年：2009
• 卷：74
• 期：17
• 页码：6735-6748
• 全文大小：1235K
• 年卷期：v.74,no.17(September 4, 2009)
• ISSN：1520-6904

文摘

The ammonium-directed olefinic oxidation of a range of cyclic allylic and homoallylic amines has been investigated. Functionalization of a range of allylic 3-(N,N-dibenzylamino)cycloalk-1-enes with m-CPBA in the presence of Cl₃CCO₂H gives exclusively the corresponding syn-epoxide for the 5-membered ring (>99:1 dr), the anti-epoxide for the 8-membered ring (>99:1 dr), and predominantly the anti-epoxide for the 7-membered ring (94:6 dr). Oxidation of the homoallylic amines 3-(N-benzylamino)methylcyclohex-1-ene and 3-(N,N-dibenzylamino)methylcyclohex-1-ene gave, in both cases, the corresponding N-protected 1,2-anti-2,3-syn-3-aminomethylcyclohexane-1,2-diol with high levels of diastereoselectivity (≥90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.