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有机光氧化还原催化α-C(sp 3 )-H 饱和杂环的磷酸化反应。

Organic photoredox catalytic α-C(sp)-H phosphorylation of saturated -heterocycles.

机构信息

State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China.

Key Laboratory of Hexi Corridor Resources Utilization of Gansu Universities, College of Chemistry and Chemical Engineering, Hexi University, Zhangye 734000, P. R. China.

出版信息

Chem Commun (Camb). 2021 Dec 7;57(97):13158-13161. doi: 10.1039/d1cc05767g.

Abstract

A metal-free C(sp)-H phosphorylation of saturated -heterocycles 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.

摘要

在温和条件下,建立了无金属的 C(sp 3 )-H 膦酸化饱和杂环的反应,该反应融合了有机光氧化还原和布朗斯台德酸催化。该方法使用商业可得的二芳基氧化膦试剂,为各种有价值的α-膦酰基环状胺提供了直接且经济的合成途径。此外,首次将 D-A 荧光分子 DCQ 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 DFT 计算表明,该转化经历了连续的可见光光氧化还原催化氧化/亲核加成过程。

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