1204-44-0Relevant articles and documents
An Approach to Tetraphenylenes via Pd-Catalyzed C-H Functionalization
Jiang, Hang,Zhang, Yu,Chen, Dushen,Zhou, Bo,Zhang, Yanghui
, p. 2032 - 2035 (2016)
Tetraphenylenes not only are theoretically and experimentally interesting but also have potential applications in a variety of fields such as materials science, supramolecular chemistry, and asymmetric catalysis. A facile and efficient approach is reported for the syntheis of tetraphenylene and its derivatives from 2-iodobiphenyls via Pd-catalyzed C-H activation. A range of substituted tetraphenylenes can be synthesized using this method, and the reaction can be performed on gram scale with relatively high efficiency, demonstrating its practical utility. This novel approach provides easy access to tetraphenylenes and should facilitate research on the application of this type of fascinating molecules.
Copper-Catalyzed Diphenylation of P(O)-OH Bonds with Cyclic Diaryliodonium Salts
Wang, Gang,Xiong, Biquan,Zhou, Congshan,Liu, Yu,Xu, Weifeng,Yang, Chang-An,Tang, Ke-Wen,Wong, Wai-Yeung
, p. 4365 - 4374 (2019)
A copper-catalyzed diphenylation of P(O)?OH bonds with cyclic diaryliodonium salts is described. Valuable 2′-iodo substituted biaryl phosphinic/phosphoric acid esters were obtained in good to excellent yields, which could be further transformed to diversified building blocks for the synthesis of bioactive compounds, pharmaceuticals and functional materials.
A Sustainable 1-Pot, 3-Step Synthesis of Boscalid Using Part per Million Level Pd Catalysis in Water
Takale, Balaram S.,Thakore, Ruchita R.,Mallarapu, Rushil,Gallou, Fabrice,Lipshutz, Bruce H.
, p. 101 - 105 (2020)
Boscalid is an active ingredient in several fungicides marketed by the BASF. Literature approaches use multipot processes, organic solvents, and unsustainable levels of palladium catalysis. Herein is disclosed a 1-pot, 3-step route using nanomicelles in water as the reaction medium and a very low loading (700 ppm or 0.07 mol %) of costly and endangered Pd. The sequence developed involves an initial Suzuki-Miyaura cross-coupling, the product from which is not isolated. The second step relies on a carbonyl iron powder (CIP) reduction of the aryl nitro group, followed by the third and final step involving an acylation with the required 2-chloronicotinyl chloride. The overall isolated yield for these three steps is 83%.
Indium powder as the reducing agent in the synthesis of 2-amino-1,1′-biphenyls
Elumalai, Vijayaragavan,Bj?rsvik, Hans-René
, p. 1224 - 1226 (2016)
An improved and simplified In-based protocol for the reduction of 2-nitro-1,1′-biphenyls to the corresponding 2-amino-1,1′-biphenyls is disclosed. The method utilizes only a stoichiometric quantity of indium powder as the reducing reagent along with a stoichiometric quantity of ammonium chloride. The work-up is very simple, it requires only a simple filtration of the post-reaction mixture whereupon the reaction medium is removed under reduced pressure. The method was also proven to operate with a variety of functional groups to provide high to excellent yields of the target 2-amino-1,1′-biphenyls. A proposal for a reaction mechanism is also provided.
An efficient water-soluble surfactant-type palladium catalyst for Suzuki cross-coupling reactions in pure water at room temperature
Qiu, Pei,Zhao, Jing Yang,Shi, Xu,Duan, Xin Hong
, p. 6568 - 6572 (2016)
A palladium catalyst based on a bidentate phosphine-type zwitterionic surfactant as a ligand exhibited an excellent catalytic activity in the Suzuki-Miyaura cross coupling reactions. This novel method allowed the reaction of aryl halides with arylboronic acids to occur in pure water at room temperature, forming a variety of biaryls in good to high yields. Heterobiaryls were also efficiently assembled even in the presence of water-insoluble heteroaryl halides as substrates. In addition, such a coupling protocol was successfully used in the iterative diarylation of 2,5-dibromopyridine in one-pot.
Synthesis method of 2-bromo-4 '-chloro-1, 1'-biphenyl
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Paragraph 0009; 0025; 0027-0028; 0031; 0032-0033; 0037; ..., (2022/03/31)
The invention belongs to the technical field of synthesis of compounds, and particularly discloses a synthesis method of 2-bromo-4 '-chloro-1, 1'-biphenyl. According to the method, aniline and parachloroiodobenzene are adopted as raw materials, an intermediate 1 is generated through a photocatalytic coupling reaction, and then the intermediate 1 is brominated through diazotization to obtain a final product. According to the method, expensive raw materials such as boric acid needed in the prior art are replaced with low-cost raw materials, the production cost is greatly reduced, and the method is energy-saving, environment-friendly, high in reaction yield in each step, simple in technological operation and suitable for technological amplification production.
Synthesis and process optimization of Boscalid by catalyst Pd-PEPPSI-IPrDtBu-An
Xu, Jian,Lan, Xiao-Bing,Xia, Lin-Jian,Yang, Yi,Cao, Gao
, p. 247 - 256 (2021/05/06)
The purpose of this research was to reduce the amount of noble metal palladium catalyst and improve the catalytic performance in the Suzuki–Miyaura cross-coupling reaction, which is the key step in the synthesis of Boscalid. Taking o-bromonitrobenzene and p-chlorophenylboronic acid as raw materials, three kinds of Pd-PEPPSI-IPr catalysts were synthesized and employed in the Suzuki reaction, and then the biaryl product was subjected to reduction and condensation reaction to give Boscalid. Under the optimal reaction conditions, the result showed that the catalytic system exhibits highest catalytic efficiency under aerobic conditions, giving the 2-(4-chlorophenyl)nitrobenzene in over 99 % yield. Moreover, the Pd-PEPPSI-IPrDtBu-An catalyst was minimized to 0.01 mol%. The synthesis process was mild, the post-treatment was simple, and the production cost was reduced, which makes it suitable for industrial production.
Regioselective Radical Arene Amination for the Concise Synthesis ofortho-Phenylenediamines
Gillespie, James E.,Morrill, Charlotte,Phipps, Robert J.
supporting information, p. 9355 - 9360 (2021/07/19)
The formation of arene C-N bonds directly from C-H bonds is of great importance and there has been rapid recent development of methods for achieving this through radical mechanisms, often involving reactiveN-centered radicals. A major challenge associated with these advances is that of regiocontrol, with mixtures of regioisomeric products obtained in most protocols, limiting broader utility. We have designed a system that utilizes attractive noncovalent interactions between an anionic substrate and an incoming radical cation in order to guide the latter to the areneorthoposition. The anionic substrate takes the form of a sulfamate-protected aniline and telescoped cleavage of the sulfamate group after amination leads directly toortho-phenylenediamines, key building blocks for a range of medicinally relevant diazoles. Our method can deliver both free amines and monoalkyl amines allowing access to unsymmetrical, selectively monoalkylated benzimidazoles and benzotriazoles. As well as providing concise access to valuableortho-phenylenediamines, this work demonstrates the potential for utilizing noncovalent interactions to control positional selectivity in radical reactions.
