δ-Selective Functionalization of Alkanols Enabled by Visible-Light-Induced Ligand-to-Metal Charge Transfer
δ-Selective Functionalization of Alkanols Enabled by Visible-Light-Induced Ligand-to-Metal Charge Transfer
复制标题
可见光诱导配体到金属电荷转移实现烷醇的δ选择性官能化
DOI：
10.1021/jacs.7b13131
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发表时间：
2018-02-07
影响因子：
15
通讯作者：
Zuo, Zhiwei
中科院分区：
文献类型：
--
作者：
Hu, Anhua;Guo, Jing-Jing;Zuo, Zhiwei
我们证明了应用配体-金属电荷转移（LMCT）激发直接催化生成的积极挑战性的烷氧基自由基从醇通过协调LMCT均裂过程与丰富和廉价的铈盐作为催化剂。这种催化歧管提供了一种简单有效的方式来利用瞬态烷氧基自由基的特征反应性和选择性用于δ-选择性C-H键官能化。在温和的氧化还原中性条件下，无需预官能化，该方法提供了一个通用的平台，从简单和丰富的醇获得分子复杂性。
We demonstrate the application of ligand-to-metal charge transfer (LMCT) excitation to the direct catalytic generation of energetically challenging alkoxy radicals from alcohols through a coordination LMCT homolysis process with an abundant and inexpensive cerium salt as the catalyst. This catalytic manifold provides a simple and efficient way to utilize the characteristic reactivity and selectivity of transient alkoxy radicals for delta-selective C-H bond functionalization. Under mild redox-neutral conditions without the need for prefunctionalizaton, this method provides a versatile platform to access molecular complexity from simple and abundant alcohols.