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.

本研究探究了一系列环状烯丙基胺及高烯丙基胺的铵导向烯烃氧化反应。对一系列烯丙基型3-(N,N-二苄基氨基)环烷-1-烯烃，在三氯乙酸（Cl₃CCO₂H）存在下与间氯过氧苯甲酸（m-CPBA）进行官能化反应时，五元环底物专一生成相应的顺式环氧化物（非对映选择性比例>99:1 dr），八元环底物专一生成反式环氧化物（>99:1 dr），七元环底物则主要生成反式环氧化物（94:6 dr）。针对高烯丙基胺类底物3-(N-苄基氨基)甲基环己-1-烯烃与3-(N,N-二苄基氨基)甲基环己-1-烯烃的氧化反应，二者均以高非对映选择性（≥90:10 dr）得到对应的N-保护1,2-反式-2,3-顺式-3-氨基甲基环己烷-1,2-二醇。上述氧化反应生成的多功能合成中间体可便捷转化为多种氨基二醇。