Copper-Catalyzed Oxaziridine-Mediated Oxidation of C鈥揌 Bonds

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• 作者：Hashim F. Motiwala ; Belgin G眉lgeze ; Jeffrey Aub茅
• 刊名：The Journal of Organic Chemistry
• 出版年：2012
• 出版时间：August 17, 2012
• 年：2012
• 卷：77
• 期：16
• 页码：7005-7022
• 全文大小：565K
• 年卷期：v.77,no.16(August 17, 2012)
• ISSN：1520-6904

文摘

The highly regio- and chemoselective oxidation of activated C鈥揌 bonds has been observed via copper-catalyzed reactions of oxaziridines. The oxidation proceeded with a variety of substrates, primarily comprising allylic and benzylic examples, as well as one example of an otherwise unactivated tertiary C鈥揌 bond. The mechanism of the reaction is proposed to involve single-electron transfer to the oxaziridines to generate a copper-bound radical anion, followed by hydrogen atom abstraction and collapse to products, with regeneration of the catalyst by a final single-electron transfer event. The involvement of allylic radical intermediates was supported by a radical-trapping experiment with TEMPO.