Copper Makes the Difference: Visible Light-Mediated Atom Transfer Radical Addition Reactions of Iodoform with Olefins
Copper Makes the Difference: Visible Light-Mediated Atom Transfer Radical Addition Reactions of Iodoform with Olefins
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DOI：
10.1021/acscatal.0c02984
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发表时间：
2020-09-04
期刊：
影响因子：
12.9
通讯作者：
Reiser, Oliver
中科院分区：
文献类型：
--
作者：
Engl, Sebastian;Reiser, Oliver
在此，我们报告了一个可见光介导的铜催化的协议，使高度经济，邻位双官能化的烯烃利用容易获得的散装化学碘仿。该方案的特征在于在环境友好的反应条件下的高产率，并允许活化双键的区域选择性和化学选择性官能化。除了所示的转换的合成效用，这项研究巩固了铜在光氧化还原催化中的独特作用，因为标题转换是不可能的，通过最常用的钌，铱，或有机染料为基础的光催化剂，由于铜的能力，以稳定和相互作用的自由基中间体在其配位领域。此外，该方案可以顺利地缩放到克量的产品，这为进一步的转化提供了多种可能性，例如，杂环合成或分子内环丙烷化。
Herein, we report a visible light-mediated copper-catalyzed protocol enabling the highly economic, vicinal difunctionalization of olefins utilizing the readily available bulk chemical iodoform. This protocol is characterized by high yields under environmentally benign reaction conditions and allows the regioselective and chemoselective functionalization of activated double bonds. Besides the synthetic utility of the shown transformation, this study undergirds the exclusive role of copper in photoredox catalysis as the title transformation is not possible via the most commonly employed ruthenium, iridium, or organic dye-based photocatalysts owing to the ability of copper to stabilize and interact with radical intermediates in its coordination sphere. Furthermore, the protocol can be smoothly scaled to gram quantities of the product, which offers manifold possibilities for further transformations, for example, heterocycle synthesis or intramolecular cyclopropanation.