92188-91-5

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• 108-86-1 bromobenzene 
• 873-76-7 para-Chlorobenzyl alcohol 
• 6630-33-7 ortho-bromobenzaldehyde 
• 106-39-8 bromochlorobenzene 
• 60081-00-7 (2-bromophenyl)(4-chlorophenyl)methanol 
• 1679-18-1 4-Chlorophenylboronic acid 
• 143238-84-0 (2-bromophenyl)methyl methanesulfonate 
• 18982-54-2 o-bromobenzyl alcohol 
• 108-90-7 chlorobenzene 
• 99585-64-5 (2-bromophenyl)(4-chlorophenyl)methanone 

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• 1379674-58-4 1-(4-chlorobenzyl)-2-ethynylbenzene 
• 4889-70-7 2-(4'-chlorobenzyl)benzoic acid 
• 98351-80-5 6-(4′-chlorophenyl)phenanthridine 

Relevant academic research and scientific papers

Copper-catalyzed aerobic double functionalization of benzylic C(sp3)-H bonds for the synthesis of 3-hydroxyisoindolinones

A copper-catalyzed aerobic 3-hydroxyisoindolinone synthesis was developed via the benzylic double C(sp3)-H functionalization of 2-alkylbenzamides. In this reaction, molecular oxygen was used as both an oxidant for C(sp3)-H functionalization and an oxygen source. Our method can be extended to diverse benzylic C(sp3)-H bonds and shows excellent functional group tolerance. This journal is

Diarylmethane synthesis through Re2O7-catalyzed bimolecular dehydrative Friedel-Crafts reactions

This manuscript describes the application of Re2O7 to the syntheses of diarylmethanes from benzylic alcohols through solvolysis followed by Friedel-Crafts alkylation. The reactions are characterized by broad substrate scope, low catalyst loadings, high chemical yields, and minimal waste generation. The intermediate perrhenate esters are superior leaving groups to chlorides and bromides in these reactions. The polarity and water sequestering capacity of hexafluoroisopropyl alcohol are critical to the success of these processes. Re2O7 is a precatalyst for HOReO3, which serves as a less costly and easily handled promoter for these reactions. Oxorhenium catalysts selectively activate alcohols in the presence of similarly substituted acetates, indicating a unique chemoselectivity and mechanism in comparison to Br?nsted acid catalysis.

Synthetic method of diarylmethanes

The invention discloses a synthetic method of diarylmethanes. The method is characterized in that benzyl pseudohalide and aromatic boric acid are reacted in an organic solvent under alkaline condition. The method employs easily available raw materials, conversion is realized under effect of no transition metal catalysis, water-free and oxygen-free are not required, Lewis acid catalysis is not required, the method has wide substrate universality, and various substituted diarylmethanes can be synthesized by the method.

Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: Turnover-limiting reductive elimination versus π-complexation

The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes-substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facilitated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron demand and conformational freedom on the rate of reductive elimination from diaryl-gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the reactivity of the arene and changes from reductive elimination to π-complexation for arenes bearing strongly electron-withdrawing substituents (σ > 0.43). Reductive elimination is accelerated by electron-donating substituents (ρ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings result in faster reductive elimination from Ar-Au(X)-Ar and lead to the π-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.

Au-Catalyzed Biaryl Coupling to Generate 5- To 9-Membered Rings: Turnover-Limiting Reductive Elimination versus ?-Complexation

The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes - substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facilitated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron demand and conformational freedom on the rate of reductive elimination from diaryl-gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the reactivity of the arene and changes from reductive elimination to ?-complexation for arenes bearing strongly electron-withdrawing substituents (σ > 0.43). Reductive elimination is accelerated by electron-donating substituents (ρ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings result in faster reductive elimination from Ar-Au(X)-Ar and lead to the ?-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.

Coupling of arylboronic acids with benzyl halides or mesylates without adding transition metal catalysts

We report herein a transition-metal-free coupling reaction of arylboronic acids with benzyl halides and mesylates for the construction of C(sp2)[sbnd]C(sp3) bonds. A unique feature of this coupling reaction is the formation regioisomers in some cases. Mechanistic studies suggest that this reaction may proceed via an unprecedented Friedel–Crafts-type reaction pathway under base conditions with the assistance of boronic acid moiety.

Efficient palladium-catalyzed C(sp2)-H activation towards the synthesis of fluorenes

A facile protocol for the synthesis of fluorene derivatives has been developed through palladium-catalyzed cyclization of 2′-halo-diarylmethanes via activation of arylic C-H bonds. The reactions occurred smoothly and allowed both electron-rich and electron-deficient substrates to convert into their corresponding fluorenes in good to excellent yields. Studies revealed that this Pd-catalyzed cyclization was also available for the substrates of 2′-chloro-diarylmethanes and no catalyst poisoning occurred for 2′-iodo-diphenylmethane.

Bismuth-catalyzed synthesis of anthracenes via cycloisomerization of o-alkynyldiarylmethane

In this study, anthracenes were efficiently synthesized from o-alkynyldiarylmethane using a novel method that exploits the synergistic effect between Bi(OTf)3 as the catalyst, and trifluoroacetic acid (TFA). Through this reaction, we achieved the rapid and efficient synthesis of anthracenes bearing various functional groups under mild conditions.

Highly efficient method for solvent-free synthesis of diarylmethane and triarylmethane from benzylic alcohols using P2O5/Al 2O3 or P2O5/SiO2 at room temperature

A highly efficient procedure for the synthesis of triarylmethane and diarylmethane via benzylation of aromatic hydrocarbons from benzyl alcohols using supported P2O5 on SiO2 and/or Al 2O3 under solvent-free conditions is described. Excellent yields of triarylmethane and diarylmethane were obtained using P 2O5-SiO2 (50%W/W) and/or P2O 5-Al2O3 (50%W/W) at room temperature. The reusability of both supported P2O5 on SiO2 and Al2O3 were examined. Both supported reagents show favorable activities in first and second runs, however, a decline in reactivity was observed in following attempts. The reaction is scalable to > 0.03 mole amounts.