99-93-4Relevant academic research and scientific papers
A copper nitride catalyst for the efficient hydroxylation of aryl halides under ligand-free conditions
Mitsudome, Takato,Mizugaki, Tomoo,Xu, Hang,Yamaguchi, Sho
supporting information, p. 6593 - 6597 (2021/08/10)
Copper nitride (Cu3N) was used as a heterogeneous catalyst for the hydroxylation of aryl halides under ligand-free conditions. The cubic Cu3N nanoparticles showed high catalytic activity, comparable to those of conventional Cu catalysts with nitrogen ligands, demonstrating that the nitrogen atoms in Cu3N act as functional ligands that promote hydroxylation.
Radical-anion coupling through reagent design: hydroxylation of aryl halides
Chechik, Victor,Greener, Andrew J.,James, Michael J.,Oca?a, Ivan,Owens-Ward, Will,Smith, George,Ubysz, Patrycja,Whitwood, Adrian C.
, p. 14641 - 14646 (2021/11/17)
The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described. Key to the success of this approach was the identification of a reducing oxime anion which can interact and couple with open-shell aryl radicals. Experimental and computational studies support the proposed radical-nucleophilic substitution chain mechanism.
Development of pH-activatable fluorescent probes for rapid visualization of metastatic tumours and fluorescence-guided surgeryviatopical spraying
Cao, Wenwen,Li, Xiaoxin,Wu, Peng,Xiong, Hu
, p. 10636 - 10639 (2021/10/19)
A series of pH-activatable aza-BODIPY-based fluorescent probes were developed for rapid cancer visualization and real-time fluorescence-guided surgery by harnessing topical spraying. These probes exhibited good water-solubility, a tunable pKafrom 5.0 to 7.9, and stable intense NIR emission at ～725 nm under acidic conditions.AzaB5with a pKavalue of 6.7 was able to rapidly and clearly visualize pulmonary and abdominal metastatic tumours including tiny metastases less than 2 mmviatopical spraying, further improving intraoperative fluorescence-guided resection. We believe thatAzaB5is promising as a powerful tool to rapidly delineate a broad range of malignancies and assist surgical tumour resection.
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.
Biocatalytic Cross-Coupling of Aryl Halides with a Genetically Engineered Photosensitizer Artificial Dehalogenase
Fu, Yu,Huang, Jian,Wu, Yuzhou,Liu, Xiaohong,Zhong, Fangrui,Wang, Jiangyun
supporting information, p. 617 - 622 (2021/02/03)
Devising artificial photoenzymes for abiological bond-forming reactions is of high synthetic value but also a tremendous challenge. Disclosed herein is the first photobiocatalytic cross-coupling of aryl halides enabled by a designer artificial dehalogenase, which features a genetically encoded benzophenone chromophore and site-specifically modified synthetic NiII(bpy) cofactor with tunable proximity to streamline the dual catalysis. Transient absorption studies suggest the likelihood of energy transfer activation in the elementary organometallic event. This design strategy is viable to significantly expand the catalytic repertoire of artificial photoenzymes for useful organic transformations.
Electrochemical-induced hydroxylation of aryl halides in the presence of Et3N in water
Ke, Fang,Lin, Chen,Lin, Mei,Long, Hua,Wu, Mei,Yang, Li,Zhuang, Qinglong
supporting information, p. 6417 - 6421 (2021/08/03)
A thorough study of mild and environmentally friendly electrochemical-induced hydroxylation of aryl halides without a catalyst is presented. The best protocol consists of hydroxylation of different aryl iodides and aryl bromides by water solution in the presence of Et3N under air, affording the target phenols in good isolated yields. Moreover, aryl chlorides were successfully employed as substrates. This methodology also provides a direct pathway for the formation of deoxyphomalone, which displayed a significant anti-proliferation effect.
Synthesis method of p-hydroxyacetophenone
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Paragraph 0030-0039, (2021/08/06)
The invention relates to the technical field of fine chemical synthesis, in particular to a synthesis method of p-hydroxyacetophenone. The synthesis method comprises the following steps of: mixing anisole and o-dichlorobenzene, then adding zinc oxide, then adding aluminum trichloride under a cooling condition, finally dropwise adding acetyl chloride, heating and stirring for reaction, cooling after reaction is finished, pouring reaction liquid into ice water for extraction and extinguishment, carrying out reduced pressure distillation to recover o-dichlorobenzene, then cooling and crystallizing, and then filtering and drying to obtain the p-hydroxyacetophenone. Under the joint promotion action of zinc oxide and aluminum trichloride, the two-step reaction of acetylation and demethylation can be continuously carried out after one-time feeding, and a real one-step synthetic reaction is realized in a one-pot way, so that the operation process is simplified, and the problems of more by-products, low yield and the like caused by inactivation of aluminum trichloride due to repeated feeding are reduced.
Rapid, chemoselective and mild oxidation protocol for alcohols and ethers with recyclable N-chloro-N-(phenylsulfonyl)benzenesulfonamide
Badani, Purav,Chaturbhuj, Ganesh,Ganwir, Prerna,Misal, Balu,Palav, Amey
supporting information, (2021/06/03)
Chlorine is the 20th most abundant element on the earth compared to bromine, iodine, and fluorine, a sulfonimide reagent, N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) was identified as a mild and selective oxidant. Without activation, the reagent was proved to oxidize primary and secondary alcohols as well as their symmetrical and mixed ethers to corresponding aldehydes and ketones. With recoverable PS-TEMPO catalyst, selective oxidation over chlorination of primary and secondary alcohols and their ethers with electron-donating substituents was achieved. The reagent precursor of NCBSI was recovered quantitatively and can be reused for synthesizing NCBSI.
Chemoselective and ligand-free aerobic oxidation of benzylic alcohols to carbonyl compounds using alumina-supported mesoporous nickel nanoparticle as an efficient recyclable heterogeneous catalyst
Das, Asit Kumar,Nandy, Sneha,Bhar, Sanjay
, (2021/05/10)
An economically efficient and operationally simple ligand-free protocol for the chemoselective oxidation of benzylic alcohols to carbonyl compounds has been developed using alumina-supported nickel nanoparticles as a stable recyclable heterogeneous catalyst along with potassium tert-butoxide in the presence of aerial oxygen as an eco-friendly oxidant. The aliphatic alcohols remained unaffected under the present condition. Excellent chemoselectivity has also been demonstrated through intermolecular and intramolecular competition experiments. This protocol accommodates a diverse range of substituents with the tolerance of various sensitive moieties during the reaction. The catalyst could be recovered by filtration and reused consecutively without any significant loss in the catalytic activity. Moreover, the heterogeneity of the catalyst has also been established by the “hot filtration method (Sheldon's test)”.
