Organic Photoredox Catalytic α-C(sp3)–H Phosphorylation of Saturated Aza-Heterocycles
Organic Photoredox Catalytic α-C(sp3)–H Phosphorylation of Saturated Aza-Heterocycles
复制标题
饱和氮杂环化合物的有机光氧化还原催化 α-C(sp3)–H 磷酸化
DOI：
10.1039/d1cc05767g
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发表时间：
2021
影响因子：
4.9
通讯作者：
Xu Guo-Qiang
中科院分区：
文献类型：
--
作者：
Yi Ming-Jun;Xiao Teng-Fei;Li Wen-Hui;Zhang Yi-Fan;Yan Pen-Ji;Zhang Baoxin;Xu Peng-Fei;Xu Guo-Qiang
在温和的条件下，通过有机光氧化还原和Brønsted酸催化的结合，建立了饱和氮杂环化合物的无金属C（sp3）-H磷酸化反应.该方案通过使用市售的二芳基氧化膦试剂提供了直接和经济的获得各种有价值的α-磷酰基环胺的途径。此外，D-A荧光分子DCQ首次用作光催化剂，并在该转化中表现出优异的光氧化还原催化效率。一系列的机理实验和密度泛函理论计算表明，这一转变经历了一个连续的可见光氧化还原催化氧化/亲核加成过程。
A metal-free C(sp3)–H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Brønsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D–A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.