365-23-1

Upstream product

• 4294-57-9 para-methylphenylmagnesium bromide 
• 106-38-7 para-bromotoluene 
• 459-32-5 (E)-4-fluorocinnamic acid 
• 350-35-6 1-(1,2-dibromoethyl)-4-fluorobenzene 
• 405-99-2 para-fluorostyrene 
• 5720-05-8 4-methylphenylboronic acid 
• 122-00-9 para-methylacetophenone 
• 460-00-4 1-Bromo-4-fluorobenzene 
• 75230-49-8 N′-(1-(4-fluorophenyl)ethylidene)-4-methylbenzenesulfonohydrazide 
• 624-31-7 4-tolyl iodide 
• 132993-23-8 4-fluorophenyl trifluoromethanesulfonate 
• 60672-33-5 4-methyl-N'-(1-(p-tolyl)ethylidene)benzenesulfonohydrazide 
• 1309603-97-1 2-(4-fluorophenyl)-2-p-tolylethanol 
• 1309603-91-5 2-((4-fluorophenyl)(p-tolyl)methyl)-1,3-dithiane 

Downstream Products

• 388-05-6 7-fluoro-4-p-tolyl-naphthalene-1,2-dicarboxylic acid-anhydride 
• 390-44-3 3-(4-fluoro-phenyl)-3-p-tolyl-acrylic acid 
• 530-46-1 4-fluoro-4'-methylbenzophenone 

Relevant academic research and scientific papers

Rhodium-Catalyzed meta-Selective C?H Carboxylation Reaction of 1,1-Diarylethylenes via Hydrorhodation-Rhodium Migration

A meta-selective C?H carboxylation reaction of 1,1-diarylethylene derivatives with CO2 by using a rhodium catalyst with NaOiPr as a stoichiometric reductant has been achieved. Together with hydrogenation of the ethylene moiety, a carboxyl group was introduced to the meta-position of the aryl ring with high selectivity over the ortho-positions. Experimental and computational mechanistic studies indicate that this carboxylation reaction proceeds via hydrorhodation on the ethylene moiety, followed by 1,4-rhodium migration and successive 1,2-rhodium migration on the aryl ring. The use of a bulky phosphine ligand seems to be the key to this unusual aryl-to-aryl 1,2-rhodium shift.

Toward a Greener Barluenga-Valdés Cross-Coupling: Microwave-Promoted C-C Bond Formation with a Pd/PEG/H2O Recyclable Catalytic System

A green Barluenga-Valdés cross-coupling reaction for the synthesis of 1,1-diarylethylenes using palladium catalysis has been developed. The new catalytic system based on Pd/Xphos-SO3Na or Pd/MeDavephos-CF3SO3 in PEG/H2O under microwave irradiation was found to be the best conditions for this transformation. The recyclability of the palladium catalyst system was also studied, and it was found to be active over nine runs without significant loss in its activity.

Cyrene as a Bio-Based Solvent for the Suzuki-Miyaura Cross-Coupling

The Suzuki-Miyaura (SM) cross-coupling is the most broadly utilized Pd-catalyzed C-C bond-forming reaction in the chemical industry. A large proportion of SM couplings employ dipolar aprotic solvents; however, current sustainability initiatives and increasingly stringent regulations advocate the use of alternatives that exhibit more desirable properties. Here we describe the scope and utility of the bio-derived solvent Cyrene in SM cross-couplings and evaluate its suitability as a reaction medium for this benchmark transformation from discovery to gram scale.

Branched Arylalkenes from Cinnamates: Selectivity Inversion in Heck Reactions by Carboxylates as Deciduous Directing Groups

A decarboxylative Mizoroki–Heck coupling of aryl halides with cinnamic acids has been developed in which the carboxylate group directs the arylation into its β-position before being tracelessly removed through protodecarboxylation. In the presence of a copper/palladium catalyst, both electron-rich and electron-deficient aryl bromides and chlorides bearing numerous functionalities were successfully coupled with broadly available cinnamates, with selective formation of 1,1-disubstituted alkenes. This reaction concept, in which the carboxylate acts as a deciduous directing group, ideally complements traditional 1,2-selective Heck reactions of styrenes.

Efficient synthesis of polysubstituted olefins using stable palladium nanocatalyst: Applications in synthesis of tamoxifen and isocombretastatin A4

A phosphine-free stable palladium nanocatalyst was used for an efficient synthesis of polysubstituted olefins from N-tosylhydrazones and aryl iodides. This methodology was successfully utilized in the synthesis of biologically important tamoxifen and isocombretastatin A4. The nanocatalyst was easily recovered and reused without any apparent loss in size and catalytic activity.

Weinreb amide based building blocks for convenient access to 1,1-diarylethenes and isocombretastatin analogues

A successful strategy based on the synthetic equivalent containing Weinreb amide functionality for the convenient access to 1,1-diarylethenes in general and for the isocombretastatin analogues in particular has been developed from the commercially available glyoxalic acid. The convenience with which the structural variations can be made in assembling the aryl residues shows generality associated with the developed strategy. The intermediates also provide access to 1,2,2-triarylethanones, represented by the synthesis of advanced intermediate of tamoxifen.