625-95-6Relevant articles and documents
Photochemically Activated Dimagnesium(I) Compounds: Reagents for the Reduction and Selective C?H Bond Activation of Inert Arenes
Jones, Dafydd D. L.,Douair, Iskander,Maron, Laurent,Jones, Cameron
supporting information, p. 7087 - 7092 (2021/03/01)
The photochemical activation of dimagnesium(I) compounds, and subsequent high yielding, regioselective reactions with inert arenes are reported. Irradiating benzene solutions of [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]?; Ar=2,6-diisopropylphenyl (Dip) or 2,4,6-tricyclohexylphenyl (TCHP)) with blue or UV light, leads to double reduction of benzene and formation of the “Birch-like” cyclohexadienediyl bridged compounds, [{(ArNacnac)Mg}2(μ-C6H6)]. Irradiation of [{(DipNacnac)Mg}2] in toluene, and each of the three isomers of xylene, promoted completely regio- and chemo-selective C?H bond activations, and formation of [(DipNacnac)Mg(Ar′)] (Ar′=meta-tolyl; 2,3-, 3,5- or 2,5-dimethylphenyl), and [{(DipNacnac)Mg(μ-H)}2]. Fluorobenzene was cleanly defluorinated by photoactivated [{(DipNacnac)Mg}2], leading to biphenyl and [{(DipNacnac)Mg(μ-F)}2]. Computational studies suggest all reactions proceed via photochemically generated magnesium(I) radicals, which reduce the arene substrate, before C?H or C?F bond activation processes occur.
Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange
Boehm, Philip,Cacherat, Bastien,Lee, Yong Ho,Martini, Tristano,Morandi, Bill
supporting information, p. 17211 - 17217 (2021/07/02)
We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C?P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.
Synthesis of biaryl compounds via Suzuki homocoupling reactions catalyzed by metal organic frameworks encapsulated with palladium nanoparticles
Bao, Yan-Sai,Cui, Xin-Yu,Han, Zheng-Bo,Li, Xin,Tang, Hong,Yang, Ming,Zhang, Yu-Yang,Zhao, Kun,Zhou, Mei-Li
, (2020/12/17)
Heterogeneous homocoupling reactions of phenylboronic acids were greatly accelerated via Suzuki homocoupling reactions. In this work, a tandem route was designed which firstly one part of phenylboronic acids reacted with iodine to form iodobenzenes, then another part of phenylboronic acids coupled with iodobenzenes to produce biaryl compounds. The tandem reaction were catalyzed by a bifunctional heterogeneous catalyst of metal organic frameworks encapsulated with palladium nanoparticles (Pd?MOFs). This strategy for forming symmetric C-C bond between benzene rings has obvious advantages such as high efficiency, easy separation, good recyclability and no addition of toxic halogenated benzene.
Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
Klein, Philippe,Lechner, Vivien Denise,Schimmel, Tanja,Hintermann, Lukas
supporting information, p. 176 - 180 (2019/12/11)
The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C?X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C?O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C?X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2–1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.
A general electrochemical strategy for the Sandmeyer reaction
Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
, p. 8731 - 8737 (2018/12/10)
Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
Direct Pd(II)-Catalyzed Site-Selective C5-Arylation of 2-Pyridone Using Aryl Iodides
Maity, Saurabh,Das, Debapratim,Sarkar, Souradip,Samanta, Rajarshi
supporting information, p. 5167 - 5171 (2018/09/13)
A straightforward Pd(II)-catalyzed general strategy was developed for the C5-selective arylation of the 2-pyridone core with easily available aryl iodides. The transformation was highly regioselective and accomplished with a wide scope and functional group tolerance. Silver nitrate played a crucial role in this direct site-selective arylation. The method was extended to synthesize biologically active molecules.
A method for synthesizing periodide (by machine translation)
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Paragraph 0005; 0009, (2017/03/18)
The invention discloses a method for synthesizing periodide, which belongs to the technical field of organic synthesis. The present invention is directed to the the periodide acrimony smell, volatile, toxicity is relatively large, and processing are not convenient, and the problem of low yield of the product, the present invention provides a method for synthesizing periodide. (by machine translation)
Method for preparing diazonium salt by utilizing micro-reactor
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Paragraph 0050; 0051, (2016/11/24)
The invention provides a method for preparing diazonium salt by utilizing a micro-reactor. The method comprises the following steps: firstly, preparing a nitrite solution and an organic amine into oil-water emulsion through a micro-mixer; enabling the oil-water emulsion to react with an introduced acid in a micro-channel to obtain the diazonium salt. The size of the salt formed by the contact of the oil-water emulsion and the acid is very small, and the salt can be consumed rapidly when reacting with nitrous acid, so that a pipeline is not blocked. The method provided by the invention is convenient and rapid to operate and short in reaction time; the defect that the diazonium salt is decomposed, caused by the fact that the temperature is too high, is avoided, and industrial production can be realized.
Easy Access to Difluoromethylene-Containing Arene Analogues through Palladium-Catalysed C–H Olefination
Shao, Changdong,Shi, Guangfa,Zhang, Yanghui
supporting information, p. 5529 - 5538 (2016/11/25)
An efficient palladium-catalysed ortho-C–H olefination of α,α-difluorophenylacetic acid derivatives using 8-aminoquinoline as a bidentate directing group has been developed. A range of olefinated arenes can thus be synthesized in a concise way. This reaction provides an easy and straightforward route to a panel of difluoromethylated arene analogues in moderate to good yields, with a satisfactory tolerance of common functional groups. Transformation of the products into a variety of other difluoromethylene-containing compounds demonstrates the utility of this method.
Rapid and efficient copper-catalyzed finkelstein reaction of (hetero)aromatics under continuous-flow conditions
Chen, Mao,Ichikawa, Saki,Buchwald, Stephen L.
supporting information, p. 263 - 266 (2015/02/05)
A general, rapid, and efficient method for the copper-catalyzed Finkelstein reaction of (hetero)aromatics has been developed using continuous flow to generate a variety of aryl iodides. The described method can tolerate a broad spectrum of functional groups, including N-H and O-H groups. Additionally, in lieu of isolation, the aryl iodide solutions were used in two distinct multistep continuous-flow processes (amidation and Mg-I exchange/nucleophilic addition) to demonstrate the flexibility of this method.
