Unactivated C(sp3)-H Bond Functionalization of Alkyl Nitriles with Vinylarenes and Mechanistic Studies.
Unactivated C(sp3)-H Bond Functionalization of Alkyl Nitriles with Vinylarenes and Mechanistic Studies.
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DOI：
10.1021/acs.orglett.6b02692
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发表时间：
2016-11
期刊：
影响因子：
5.2
通讯作者：
Xing-Wang Lan;Naixing Wang;Cui-Bing Bai;Cui-Lan Lan-Cui-Lan-Lan-39767273;Tong Zhang;Shi‐Lu Chen;Yalan Xing
中科院分区：
文献类型：
--
作者：
Xing-Wang Lan;Naixing Wang;Cui-Bing Bai;Cui-Lan Lan-Cui-Lan-Lan-39767273;Tong Zhang;Shi‐Lu Chen;Yalan Xing
描述了烷基腈与末端乙烯基芳烃的无金属未活化C（sp3）-H键官能化以提供γ-酮腈衍生物的第一个实例。该方法具有操作简单、底物范围广、原子和步骤经济等特点。此外，还研究了Cu催化的偶氮二异丁腈（AIBN）及其类似物的C（sp3）-H键功能化反应生成γ-酮腈。初步的自由基途径被证实捕获的烷基自由基，并发现共轭体系，可以稳定自由基中间体，有利于这种转变。密度泛函理论（DFT）计算也提供了自由基途径的重要证据。
The first example of a metal-free unactivated C(sp3)-H bond functionalization of alkyl nitriles with terminal vinylarenes to provide γ-ketonitrile derivatives is described. This protocol features simple operations, a broad substrate scope, and atom and step economy. In addition, Cu-catalyzed C(sp3)-H bond functionalization of azodiisobutyronitrile (AIBN) and analogues with terminal vinylarenes to generate γ-ketonitriles was also studied. A preliminary free-radical pathway was confirmed by capturing an alkyl radical, and a conjugate system was found that can stabilize radical intermediates and be in favor of this transformation. Density functional theory (DFT) calculations also provide important evidence of the free-radical pathway.