66052-06-0Relevant articles and documents
Discovery and characterization of a novel perylenephotoreductant for the activation of aryl halides
Guo, Baodang,Huang, Shuping,Li, Jia,Li, Min,Liu, Xuanzhong,Rao, Yijian,Wu, Yawen,Yin, Huimin,Yuan, Zhenbo,Zhang, Yan
, p. 111 - 120 (2021/06/16)
To develop a photocatalyst with catalytical activity for substrates with low reactivities is always highly desired. Herein, based on the principle of structure–property relationships, we rationally designed the natural product cercosporin, the naturally occurring perylenequinonoid pigment, to develop a novel organic perylenephotoreductant, hexacetyl reduced cercosporin (HARCP), through structural manipulation. Compared with cercosporin, HARCP shows prominent electrochemical and photophysical characteristics with greatly improved photoreductive activity, fluorescence lifetime and fluorescence quantum yield. These properties allowed HARCP as a powerful photoreductant to efficiently realize a series of benchmark reactions, including photoreduction, alkoxylation and hydroxylation to construct C–H and C–O bonds using aryl halides as substrates under mild conditions, all of which have never been achieved by the same photocatalyst. Thus, this study well supports the notion that the principle between structural manipulation and photocatalytic activity is of great significance to design customized photocatalysts for photoredox chemistry.
Oxalohydrazide Ligands for Copper-Catalyzed C?O Coupling Reactions with High Turnover Numbers
Ray, Ritwika,Hartwig, John F.
supporting information, p. 8203 - 8211 (2021/03/08)
Here, we report a class of ligands based on oxalohydrazide cores and N-amino pyrrole and N-amino indole units that generates long-lived copper catalysts for couplings that form the C?O bonds in biaryl ethers. These Cu-catalyzed coupling of phenols with aryl bromides occurred with turnovers up to 8000, a value which is nearly two orders of magnitude higher than those of prior couplings to form biaryl ethers and nearly an order of magnitude higher than those of any prior copper-catalyzed coupling of aryl bromides and chlorides. This ligand also led to copper systems that catalyze the coupling of aryl chlorides with phenols and the coupling of aryl bromides and iodides with primary benzylic and aliphatic alcohols. A wide variety of functional groups including nitriles, halides, ethers, ketones, amines, esters, amides, vinylarenes, alcohols and boronic acid esters were tolerated, and reactions occurred with aryl bromides in pharmaceutically related structures.
Metal-organic layers as multifunctional two-dimensional nanomaterials for enhanced photoredox catalysis
Lan, Guangxu,Quan, Yangjian,Wang, Maolin,Nash, Geoffrey T.,You, Eric,Song, Yang,Veroneau, Samuel S.,Jiang, Xiaomin,Lin, Wenbin
supporting information, p. 15767 - 15772 (2019/10/11)
Metal-organic layers (MOLs) have recently emerged as a novel class of molecular two-dimensional (2D) materials with significant potential for catalytic applications. Herein we report the design of a new multifunctional MOL, Hf12-Ir-Ni, by laterally linking Hf12 secondary building units (SBUs) with photosensitizing Ir(DBB)[dF(CF3)ppy]2+ [DBB-Ir-F, DBB = 4,4′-di(4-benzoato)-2,2′-bipyridine; dF(CF3)ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine] bridging ligands and vertically terminating the SBUs with catalytic Ni(MBA)Cl2 [MBA = 2-(4′-methyl-[2,2′-bipyridin]-4-yl)acetate] capping agents. Hf12-Ir-Ni was synthesized in a bottom-up approach and characterized by TEM, AFM, PXRD, TGA, NMR, ICP-MS, UV-vis, and luminescence spectroscopy. The proximity between photosensitizing Ir centers and catalytic Ni centers (～0.85 nm) in Hf12-Ir-Ni facilitates single electron transfer, leading to a 15-fold increase in photoredox reactivity. Hf12-Ir-Ni was highly effective in catalytic C-S, C-O, and C-C cross-coupling reactions with broad substrate scopes and turnover numbers of ～4500, ～1900, and ～450, respectively.
