170789-13-6Relevant academic research and scientific papers
Palladium-catalyzed desulfitative cross-coupling reaction of sodium sulfinates with benzyl chlorides
Zhao, Feng,Tan, Qi,Xiao, Fuhong,Zhang, Shufeng,Deng, Guo-Jun
, p. 1520 - 1523 (2013)
A palladium-catalyzed approach for the synthesis of diarylmethanes from sodium sulfinates and benzyl chlorides is described. Various aromatic sodium sulfinates were used as aryl sources via extrusion of SO2 and gave the diarylmethanes in moderate to good yields.
Mixed Alkyl/Aryl Diphos Ligands for Iron-Catalyzed Negishi and Kumada Cross Coupling Towards the Synthesis of Diarylmethane
Ma, Xufeng,Wang, Han,Liu, Yao,Zhao, Xing,Zhang, Jun
, p. 5134 - 5140 (2021/11/16)
Mixed alkyl/aryl diphos ligands have been prepared and their application in iron-catalyzed cross coupling of benzylic chlorides with diaryl zinc (Negishi) or aryl Grignard reagents (Kumada) towards the synthesis of diarylmethane has been evaluated. The iron?diphos catalytic system exhibited the enhanced activity and selectivity in the two coupling reactions. The electron-rich mixed PPh2/PCy2 ligands outperformed their symmetrical PPh2 congeners, and led to decreased homocoupling byproduct formation. It indicates that the electronic effect of the ligands plays an important role in the catalytic performance. The Fe catalyst supported by L8 bearing an electron-rich PCy2 substituent and a sterically demanding tert-butyl on ethene backbone exhibited the best catalytic performance and good functional group tolerance in the two cross coupling reactions.
Heteroleptic Ni(II) Complexes Bearing a Bulky Yet Flexible IBiox-6 Ligand: Improved Selectivity in Cross-Electrophile Coupling of Benzyl Chlorides with Aryl Chlorides/Fluorides
Shen, Zheng-Wang,Meng, Die-Die,Imran, Sajid,Yan, Chun-Hui,Sun, Hong-Mei
supporting information, p. 3540 - 3545 (2020/10/09)
A bisoxazoline-derived NHC known as IBiox-6 reacted smoothly with Ni[P(OEt)3]2Br2 and Ni(PPh3)2Br2 to give the respective heteroleptic Ni(II) complexes Ni(IBiox-6)[P(OEt)3]Br2 (1) and Ni(IBiox-6)(PPh3)Br2 (2) in yields of 60% and 71%. Their crystal structures were characterized to reveal a rare cis disposition of the IBiox-6 ligand to the phosphite ligand in 1, while 2 possessed the more common trans configuration. Both complexes catalyzed the cross-electrophile coupling of benzyl chlorides with aryl chlorides and fluorides in the presence of Mg turnings at 50 °C via a "real one-pot"procedure, featuring no requirement for temperature variation or portionwise addition of any coupling partner. In particular, complex 1 showed a better balance between the catalytic activity and selectivity. The scope of the procedure catalyzed by 1 and Mg turnings was investigated, providing a highly selective, simple, and practical approach to the synthesis of diarylmethanes with high steric hindrance and various functional groups, including oligo-diarylmethane with asymmetric structures.
Preparation and application of blended nickel (II) complex with bisoxazoline derived azacyclo-carbene ligand and phosphite ester ligand
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Paragraph 0044-0045, (2019/10/17)
The invention discloses a blended nickel (II) complex with a bisoxazoline derived azacyclo-carbene ligand and a phosphite ester ligand and application of the blended nickel (II) complex. The blended nickel (II) complex has a chemical formula of Ni(NHC)[P(OR)3]X2, in the formula, R is one of ethyl or isopropyl; X is one of bromine atoms or helium atoms; and NHC is the bisoxazoline derived azacyclo-carbene ligand. In the presence of magnesium chips, the blended nickel (II) complex with the bisoxazoline derived azacyclo-carbene ligand and the phosphite ester ligand, which is disclosed by the invention, is capable of catalyzing aromatic hydrocarbon or fluoro-aromatic hydrocarbon with low activity to have a reduction cross coupling reaction with a benzyl chloride type compound at a single temperature, then a diarylmethane compound can be generated at one step, and a novel method is provided for synthesizing diarylmethane compounds.
N-heterocyclic carbene–palladium complexes for Suzuki–Miyaura coupling reaction with benzyl chloride and aromatic boronic acid leading to diarylmethanes
Chen, Ming-Tsz,Wang, Wan-Rong,Li, Yi-Jun
, (2019/04/08)
A family of N-heterocyclic carbene–palladium(II)–N,N-dimethylbenzylamine complexes ((NHC)LPdCl2; L?=?N,N-dimethylbenzylamine) were synthesized as well as characterized using single-crystal X-ray diffraction and spectroscopic data. These complexes exhibited higher catalytic activities for the Suzuki reaction of benzyl chlorides to afford diarylmethanes under milder conditions than other efficient (NHC)LPdCl2 complexes. Using the optimum conditions, the expected coupling products were obtained in moderate to high yields. All reactions were carried out in air and all starting materials were used as supplied without purification.
An Efficient Ga(OTf)3/Isopropanol Catalytic System for Direct Reduction of Benzylic Alcohols
Sai, Masahiro
, p. 4330 - 4335 (2018/10/15)
This study aims to report the first gallium-catalyzed direct reduction of benzylic alcohols using isopropanol as a reductant. The reaction proceeds via gallium catalyst-assisted hydride transfer of the in situ-generated benzylic isopropyl ether. The method generates only water and acetone as byproducts and thus provides an atom-economic and environmentally friendly approach to the synthesis of di- and triarylmethanes, which are important substructures in various bioactive compounds and functional materials. (Figure presented.).
Substrate switchable Suzuki-Miyaura coupling for benzyl ester: Vs. benzyl halide
Ohsumi, Masato,Ito, Akitaka,Nishiwaki, Nagatoshi
, p. 35056 - 35061 (2018/10/24)
Two reaction conditions were developed to accomplish the substrate switchable Suzuki-Miyaura coupling of benzyl derivatives and arylboronic acid derivatives. Under conditions for esters, benzyl esters such as carbonates and acetates reacted with arylboronic acids to afford the corresponding diarylmethanes. However, the benzyl halides did not react under the same conditions. On the other hand, benzyl halides such as bromides and chlorides furnished diarylmethanes under conditions for halides, under which benzyl ester substrates did not react, in which water was found to play an important role. This switching system was tested using the intermolecular/intramolecular competitive reactions, during which the desired products could be synthesized by selecting the appropriate reaction conditions.
A Zinc Catalyzed C(sp3)?C(sp2) Suzuki–Miyaura Cross-Coupling Reaction Mediated by Aryl-Zincates
Procter, Richard J.,Dunsford, Jay J.,Rushworth, Philip J.,Hulcoop, David G.,Layfield, Richard A.,Ingleson, Michael J.
, p. 15889 - 15893 (2017/10/24)
The Suzuki–Miyaura (SM) reaction is one of the most important methods for C?C bond formation in chemical synthesis. In this communication, we show for the first time that the low toxicity, inexpensive element zinc is able to catalyze SM reactions. The cross-coupling of benzyl bromides with aryl borates is catalyzed by ZnBr2, in a process that is free from added ligand, and is compatible with a range of functionalized benzyl bromides and arylboronic acid pinacol esters. Initial mechanistic investigations indicate that the selective in situ formation of triaryl zincates is crucial to promote selective cross-coupling reactivity, which is facilitated by employing an arylborate of optimal nucleophilicity.
Iron phosphine catalyzed cross-coupling of tetraorganoborates and related group 13 nucleophiles with alkyl halides
Bedford, Robin B.,Brenner, Peter B.,Carter, Emma,Clifton, Jamie,Cogswell, Paul M.,Gower, Nicholas J.,Haddow, Mairi F.,Harvey, Jeremy N.,Kehl, Jeffrey A.,Murphy, Damien M.,Neeve, Emily C.,Neidig, Michael L.,Nunn, Joshua,Snyder, Benjamin E. R.,Taylor, Joseph
, p. 5767 - 5780 (2015/02/19)
Iron phosphine complexes prove to be good precatalysts for the cross-coupling of alkyl, benzyl, and allyl halides with not only aryl triorganoborate salts but also related aluminum-, gallium-, indium-, and thallium-based nucleophiles. Mechanistic studies revealed that while Fe(I) can be accessed on catalytically relevant time scales, lower average oxidation states are not formed fast enough to be relevant to catalysis. EPR spectroscopic studies reveal the presence of bis(diphosphine)iron(I) complexes in representative catalytic reactions and related processes with a range of group 13 nucleophiles. Isolated examples were studied by M?ssbauer spectroscopy and single-crystal X-ray structural analysis, while the electronic structure was probed by dispersion-corrected B3LYP DFT calculations. An EPR study on an iron system with a bulky diphosphine ligand revealed the presence of an S = 1/2 species consistent with the formation of a mono(diphosphine)iron(I) species with inequivalent phosphine donor environments. DFT analysis of model complexes allowed us to rule out a T-shaped Fe(I) structure, as this is predicted to be high spin.
Nickel-catalyzed cross couplings of benzylic ammonium salts and boronic acids: Stereospecific formation of diarylethanes via C-N bond activation
Maity, Prantik,Shacklady-Mcatee, Danielle M.,Yap, Glenn P. A.,Sirianni, Eric R.,Watson, Mary P.
supporting information, p. 280 - 285 (2013/02/25)
We have developed a nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids to afford diarylmethanes and diarylethanes. This reaction proceeds under mild reaction conditions and with exceptional functional group tolerance. Further, it transforms branched benzylic ammonium salts to diarylethanes with excellent chirality transfer, offering a new strategy for the synthesis of highly enantioenriched diarylethanes from readily available chiral benzylic amines.
