Acid-catalyzed oxidative radical addition of ketones to olefins.
Acid-catalyzed oxidative radical addition of ketones to olefins.
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DOI：
10.1002/anie.201401062
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发表时间：
2014-08
影响因子：
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通讯作者：
Bertrand Schweitzer‐Chaput;J. Demaerel;Hauke Engler;M. Klussmann
中科院分区：
文献类型：
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作者：
Bertrand Schweitzer‐Chaput;J. Demaerel;Hauke Engler;M. Klussmann
在机理研究的基础上，我们发现了一种Brnsted酸催化酮自由基的形成。这被认为是通过酮和过氧化氢原位生成的热不稳定的烯基过氧化物所进行的。这一发现可用于开发未活化酮和叔丁基氢过氧化氢与烯烃的多组分自由基加成反应。生成的γ-过氧基酮是合成上有用的中间体，可以进一步转化为1，4-二酮、高甲醛产物和烷基酮。还描述了一锅反应产生具有药用活性的吡咯。
Based on a mechanistic study, we have discovered a Brønsted acid catalyzed formation of ketone radicals. This is believed to proceed via thermally labile alkenyl peroxides formed in situ from ketones and hydroperoxides. The discovery could be utilized to develop a multicomponent radical addition of unactivated ketones and tert-butyl hydroperoxide to olefins. The resulting γ-peroxyketones are synthetically useful intermediates that can be further transformed into 1,4-diketones, homoaldol products, and alkyl ketones. A one-pot reaction yielding a pharmaceutically active pyrrole is also described.