State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12619-12623. doi: 10.1002/anie.201707171. Epub 2017 Sep 4.
The alkoxyl radical is an essential and prevalent reactive intermediate for chemical and biological studies. Here we report the first donor-acceptor complex-enabled alkoxyl radical generation under metal-free reaction conditions induced by visible light. Hantzsch ester forms the key donor-acceptor complex with N-alkoxyl derivatives, which is elucidated by a series of spectrometry and mechanistic experiments. Selective C(sp )-C(sp ) bond cleavage and allylation/alkenylation is demonstrated for the first time using this photocatalyst-free approach with linear primary, secondary, and tertiary alkoxyl radicals.
烷氧基自由基是化学和生物学研究中必不可少且普遍存在的反应中间体。在这里，我们报道了首例在可见光诱导下、无金属反应条件下形成的供体-受体复合物促进的烷氧基自由基生成。通过一系列光谱和机理实验，阐明了 Hantzsch 酯与 N-烷氧基衍生物形成关键的供体-受体复合物。首次使用这种无光催化剂的方法，以线性伯、仲和叔烷氧基自由基为底物，实现了 C(sp )-C(sp )键选择性断裂以及烯丙基化/烷基化反应。
