Activation of N-sulfonyl oxaziridines using copper(II) catalysts:: Aminohydroxylations of styrenes and 1,3-dienes
Activation of N-sulfonyl oxaziridines using copper(II) catalysts:: Aminohydroxylations of styrenes and 1,3-dienes
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DOI：
10.1021/ja800495r
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发表时间：
2008-05-21
影响因子：
15
通讯作者：
Yoon, Tehshik P.
中科院分区：
文献类型：
--
作者：
Michaelis, David J.;Ischay, Michael A.;Yoon, Tehshik P.
N-磺酰基氧氮杂环丙烷对使用铜（II）催化剂的亲电活化敏感，并且在这些条件下与苯乙烯反应以在烯烃的形式氨羟基化中提供1，3-恶唑烷。我们提出了一个两步机制，涉及阳离子中间体占使用各种苯乙烯观察到的速率差异和区域选择性。与我们的假设雅阁，一系列带有电子稳定基团的底物的amirlohydroxylations是成功的，并且1，3-二烯是铜（II）催化的氨羟基化的特别好的底物。不对称二烯的反应提供了良好到优异的烯烃选择性，其意义和大小可以在考虑由我们的机制建议的阳离子中间体的稳定性后合理化。通过使用氨羟基化作为关键的复杂性增加步骤的二烯的多官能化，可以实现各种各样的密集官能化结构的非对映选择性合成。
N-Sulfonyl oxaziridines are susceptible to electrophilic activation using copper(II) catalysts and react with styrenes under these conditions to provide 1,3-oxazolidines in a formal aminohydroxylation of the alkene. We propose a two-step mechanism involving a cationic intermediate to account for the rate differences and regioselectivities observed using a variety of styrenes. In accord with our hypothesis, amirlohydroxylations of a range of substrates bearing electron-stabilizing groups are successful, and 1,3-dienes are particularly good substrates for copper(II)-catalyzed aminohydroxylation. Reactions of unsymmetrical dienes provide good to excellent olefin selectivity, the sense and magnitude of which can be rationalized upon consideration of the stability of the cationic intermediates suggested by our mechanism. Diastereoselective synthesis of a diverse range of densely functionalized structures can be achieved by polyfunctionalization of dienes using aminohydroxylation as a key complexity-increasing step.