22865-60-7

Upstream product

• 766-77-8 Dimethylphenylsilane 
• 429677-37-2 (p-methoxyphenyl)(p-tolyl)methylium cation 
• 3395-83-3 4-methylbenzaldehyde dimethylacetal 
• 100-66-3 methoxybenzene 
• 104-82-5 4-Methylbenzyl chloride 
• 789-25-3 HSiPh₃ 
• 123-11-5 4-methoxy-benzaldehyde 
• 108-88-3 toluene 
• 39619-60-8 trans,trans-2,5-Heptadien 
• 106-43-4 para-chlorotoluene 
• 38769-92-5 4-methoxybenzylmagnesium chloride 
• 838-22-2 4-methoxy-4'-methylbenzhydrol 
• 67-63-0 isopropyl alcohol 
• 714223-44-6 4-methoxy-4'-methylbenzhydryl 3,5-dinitrobenzoate 

Downstream Products

• 429677-37-2 (p-methoxyphenyl)(p-tolyl)methylium cation 
• 33667-91-3 N-(4-methoxyphenyl)-4-methylbenzamide 
• 39192-94-4 N-(p-methylphenyl)-p-methoxybenzamide 
• 116664-87-0 (4-methylphenyl)-(4'-methoxyphenyl)methyl acetate 
• 134310-99-9 4-(4-methoxyphenyl)-4-(4-methylphenyl)-1-butene 
• 28994-46-9 4-(4-methylbenzyl)phenol 

Relevant academic research and scientific papers

A novel and efficient route to diarylmethanes catalyzed by nickel(II) ion on nanoporous carbon

Much improved catalytic carbon-carbon bond-forming reactions between aryl chlorides and Grignard reagents has been achieved using nickel(II) ion on nanoporous carbon.

Palladium-catalyzed cross-coupling of benzyltitanium(IV) reagents with aryl fluorides

The first palladium-catalyzed cross-coupling between benzyltitanium(IV) reagents with aryl fluorides is reported. A variety of diarylmethanes can be prepared in good to excellent yields by the catalyst system of PdCl2(dppf)2 associated with 1-[2-(di-tert-butylphosphanyl)phenyl]-4-methoxypiperidine. This reaction offered a highly efficient approach to diarylmethanes that are commonly found in life-changing drug molecules. Graphical abstract: [Figure not available: see fulltext.]

Dynamic Kinetic Cross-Electrophile Arylation of Benzyl Alcohols by Nickel Catalysis

Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report a dynamic kinetic cross-coupling approach for the direct functionalization of alcohols. The feasibility of this strategy is demonstrated by a nickel-catalyzed cross-electrophile arylation reaction of benzyl alcohols with (hetero)aryl electrophiles. The reaction proceeds with a broad substrate scope of both coupling partners. The electron-rich, electron-poor, and ortho-/meta-/para-substituted (hetero)aryl electrophiles (e.g., Ar-OTf, Ar-I, Ar-Br, and inert Ar-Cl) all coupled well. Most of the functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar-SiMe3, Ar-Bpin, and Ar-SnBu3, were tolerated. The dynamic nature of this method enables the direct arylation of benzylic alcohol in the presence of various nucleophilic groups, including nonactivated primary/secondary/tertiary alcohols, phenols, and free indoles. It thus offers a robust alternative to existing methods for the precise construction of diarylmethanes. The synthetic utility of the method was demonstrated by a concise synthesis of biologically active molecules and by its application to peptide modification and conjugation. Preliminary mechanistic studies revealed that the reaction of in situ formed benzyl oxalates with nickel, possibly via a radical process, is an initial step in the reaction with aryl electrophiles.

Mixed Alkyl/Aryl Diphos Ligands for Iron-Catalyzed Negishi and Kumada Cross Coupling Towards the Synthesis of Diarylmethane

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.

Method for synthesizing diaryl methane derivative

The invention aims to provide a method for synthesizing a diaryl methane derivative. The method is characterized in that tris (dibenzylideneacetone) dipalladium is used as a catalyst, an organic antimony compound is used as a nucleophilic reagent, benzyl bromide and benzyl chloride are used as electrophilic reagents, toluene is used as a solvent, and the diaryl methane derivative is synthesized through direct cross coupling under the air atmosphere condition. The method has the characteristics of good substrate universality, good functional group tolerance, simplicity and convenience in operation and the like.

Nickel catalyzed deoxygenative cross-coupling of benzyl alcohols with aryl-bromides

A nickel-catalyzed cross-electrophile coupling of benzyl alcohols with aromatic bromides has been developed. This deoxygenative cross-coupling occurs under mild reaction conditions at ambient temperature affording diarylmethanes, or 1,3-diarylpropenes from benzyl allyl alcohols. The system demonstrated good chemoselectivity tolerating an assortment of reactive functional groups.

Ligand-Facilitated Reductive Coupling of Benzyl Chlorides with Aryl Chlorides Catalyzed by Well-Defined Heteroleptic Ni (II)-NHC Complexes

Novel heteroleptic Ni (II) complexes bearing a highly hindered yet flexible IPr* ligand, Ni (IPr*)(PPh3)Br2 (1) and Ni (IPr*)(PCy3)Br2 (2) (IPr* = 1,3-bis(2,6-bis (diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene), were easily prepared in 78percent and 89percent yield, respectively. Both were characterized by elemental analysis and NMR spectroscopy, and 1 was subjected to X-ray crystallography. Compared with 2 and its analogue bearing a less sterically demanding IPr ligand (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), complex 1 exhibited superior catalytic activity in the magnesium-mediated reductive coupling of benzyl chlorides with aryl chlorides, featuring outstanding tolerance of both coupling partners with steric demand. This study discloses a ligand-facilitated reductive coupling of benzyl chlorides with aryl chlorides, which provides a new and practical synthetic tool for the synthesis of diarylmethanes.

Nickel catalysis enables convergent paired electrolysis for direct arylation of benzylic C-H bonds

Convergent paired electrosynthesis is an energy-efficient approach in organic synthesis; however, it is limited by the difficulty to match the innate redox properties of reaction partners. Here we use nickel catalysis to cross-couple the two intermediates

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

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.

N-heterocyclic carbene–palladium complexes for Suzuki–Miyaura coupling reaction with benzyl chloride and aromatic boronic acid leading to diarylmethanes

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.