State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology , Hangzhou, Zhejiang 310014, P. R. China.
Department of Materials Science and Engineering, Arizona State University , Tempe, Arizona 85284, United States.
J Org Chem. 2017 Aug 18;82(16):8634-8644. doi: 10.1021/acs.joc.7b01568. Epub 2017 Aug 7.
An efficient and practical CuCl-catalyzed hydroxylation of N-heteroarylcarbazole bromide for the preparation of N-heteroarylcarbazolyl phenols with a broad functional group scope and yield up to 98% was developed. It was found that both the ligand and base played critical roles in the functional group transformation and that different products could be generated by changing the base for some substrates. t-BuONa was demonstrated to be a better base for the catalytic system to avoid the formation of the ether byproduct. In addition, this approach was suitable for large-scale preparation and was successfully applied in the gram-scale synthesis of phosphorescent emitters PtNON and PdNON, demonstrating its practicability in organic synthesis methodology and materials science. Furthermore, the X-ray crystal diffraction, DFT calculations, and photophysical properties were also investigated for the metal complexes.
开发了一种高效实用的 CuCl 催化 N-杂芳基咔唑溴的羟基化反应，用于制备具有广泛官能团范围的 N-杂芳基咔唑基酚，产率高达 98%。研究发现，配体和碱在官能团转化中都起着关键作用，通过改变一些底物的碱，可以生成不同的产物。t-BuONa 被证明是催化体系中更好的碱，可以避免醚副产物的形成。此外，该方法适用于大规模制备，并成功应用于磷光发射体 PtNON 和 PdNON 的克级合成，证明了其在有机合成方法学和材料科学中的实用性。此外，还对金属配合物进行了 X 射线晶体衍射、DFT 计算和光物理性质研究。
