Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines

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.本研究针对一系列环状烯丙基胺与高烯丙基胺的铵导向烯烃氧化反应开展了系统探究。以间氯过氧苯甲酸（m-CPBA）为氧化剂，在三氯乙酸（Cl3CCO2H）存在的条件下，对一系列烯丙基3-(N,N-二苄基氨基)环烷基-1-烯烃进行官能化反应时，五元环底物仅生成对应的顺式环氧化物（非对映选择性比例>99:1），八元环底物仅生成反式环氧化物（>99:1 dr），七元环底物则主要生成反式环氧化物（94:6 dr）。针对高烯丙基胺3-(N-苄基氨基)甲基环己-1-烯与3-(N,N-二苄基氨基)甲基环己-1-烯的氧化反应，两种底物均以优异的非对映选择性（≥90:10 dr）得到对应的N-保护型1,2-反式-2,3-顺式-3-氨甲基环己烷-1,2-二醇。经由上述氧化反应得到的多用途合成中间体，可便捷地转化为一系列氨基二醇类化合物。