Reaction of CuI with Dialkyl Peroxides: CuII-Alkoxides, Alkoxy Radicals, and Catalytic C鈥揌 Etherification

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• 作者：Raymond T. Gephart ; III ; Claire L. McMullin ; Nicholas G. Sapiezynski ; Eun Sil Jang ; Mae Joanne B. Aguila ; Thomas R. Cundari ; Timothy H. Warren
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：October 24, 2012
• 年：2012
• 卷：134
• 期：42
• 页码：17350-17353
• 全文大小：310K
• 年卷期：v.134,no.42(October 24, 2012)
• ISSN：1520-5126

文摘

Kinetic analysis of the reaction of the copper(I) 尾-diketiminate [Clb>2b>NN]Cu ([Cu^I]) with ^tBuOO^tBu to give [Cu^II]鈥揙^tBu (<b>1b>) reveals first-order behavior in each component implicating the formation of free ^tBuO^{鈥?/sup> radicals. Added pyridine mildly inhibits this reaction indicating competition between tBuOOtBu and py for coordination at [CuI] prior to peroxide activation. Reaction of [CuI] with dicumyl peroxide leads to [CuII]鈥揙CMeb>2b>Ph (<b>3b>) and acetophenone suggesting the intermediacy of the PhMeb>2b>CO鈥?/sup> radical. Computational methods provide insight into the activation of tBuOOtBu at [CuI]. The novel peroxide adduct [CuI](tBuOOtBu) (<b>4b>) and the square planar [CuIII](OtBu)b>2b> (<b>5b>) were identified, each unstable toward loss of the tBuO鈥?/sup> radical. Facile generation of the tBuO鈥?/sup> radical is harnessed in the catalytic C鈥揌 etherification of cyclohexane with tBuOOtBu at rt employing [CuI] (5 mol %) to give the ether Cy鈥揙tBu in 60% yield.}