Bond Christopher W, Cresswell Alexander J, Davies Stephen G, Fletcher Ai M, Kurosawa Wataru, Lee James A, Roberts Paul M, Russell Angela J, Smith Andrew D, Thomson James E
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK.
J Org Chem. 2009 Sep 4;74(17):6735-48. doi: 10.1021/jo9012783.
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 Cl(3)CCO(2)H 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 (>or=90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.
已对一系列环状烯丙基胺和高烯丙基胺的铵导向烯属氧化反应进行了研究。在三氯乙酸存在下，用间氯过氧苯甲酸对一系列烯丙基3-(N,N-二苄基氨基)环烷-1-烯进行官能化反应，对于五元环，仅生成相应的顺式环氧化物（非对映体比例>99:1）；对于八元环，生成反式环氧化物（非对映体比例>99:1）；对于七元环，主要生成反式环氧化物（非对映体比例94:6）。高烯丙基胺3-(N-苄基氨基)甲基环己-1-烯和3-(N,N-二苄基氨基)甲基环己-1-烯的氧化反应，在两种情况下均生成具有高非对映选择性（非对映体比例≥90:10）的相应N-保护的1,2-反式-2,3-顺式-3-氨基甲基环己烷-1,2-二醇。这些氧化反应产生的通用合成中间体可很容易地转化为一系列氨基二醇。
