1611-86-5

Upstream product

• 403-42-9 1-(4-fluorophenyl)ethanone 
• 100-52-7 benzaldehyde 
• 1611-84-3 5-(4-fluorophenyl)-3-phenyl-4,5-dihydro-1H-pyrazole 
• 1608-51-1 4-fluorochalcone 
• 405-99-2 para-fluorostyrene 
• 100-42-5 styrene 
• 210422-66-5 4-fluorobenzaldehyde p-toluenesulfonylhydrazone 
• 459-57-4 4-fluorobenzaldehyde 
• 1666-17-7 benzaldehyde p-toluenesulfonylhydrazone 
• 908094-04-2 phenyldiazomethane 
• 536-74-3 phenylacetylene 
• 1200806-90-1 1-(octane-1-sulfonyl)-4-phenyl-1H-1,2,3-triazole 
• 352-34-1 4-fluoro-1-iodobenzene 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 

Downstream Products

• 56363-45-2 1-(p-Fluorphenyl)-2-phenyl-1,3-dibrompropan 

Relevant academic research and scientific papers

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon-Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated as a promising synthetic method. However, dicarboxylation of C-C single bonds with CO2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of C-C single bonds in strained rings with CO2. Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.

Reductive Ring-Opening 1,3-Difunctionalizations of Arylcyclopropanes with Sodium Metal

Sodium dispersion promotes reductive ring opening of arylcyclopropanes. The presence of a reduction-resistant electrophile, such as methoxypinacolatoborane, epoxide, oxetane, paraformaldehyde, or chlorotrimethylsilane, during the reductive ring opening event leads to the formation of 1,3-difunctionalized 1-arylalkanes by immediate trappings of the resulting two reactive carbanions. In particular, the ring-opening 1,3-diborylations of arylcyclopropanes afford 1,3-diborylalkanes with high syn selectivity.

Enantioselective Cyclobutenylation of Olefins Using N-Sulfonyl-1,2,3-Triazoles as Vicinal Dicarbene Equivalents

Cyclobutenes are highly useful synthetic intermediates as well as important motifs in bioactive small molecules. Herein, we report a regio-, chemo-, and enantioselective synthesis of cyclobutenes from olefins using N-sulfonyl-1,2,3-triazoles as vicinal dicarbene equivalents or alkyne [2 + 2] cycloaddition surrogates. Terminal and cis-olefins can be transformed into enantioenriched cyclopropanes via rhodium catalysis. Then, in one pot, treatment of these intermediates with tosyl hydrazide and base effects diazo formation followed by rhodium-catalyzed ring expansion to yield enantioenriched cyclobutenes. These cyclobutenes can be transformed into highly substituted, enantioenriched cyclobutanes, including structures relevant to natural product scaffolds.

Iron-catalyzed synthesis of cyclopropanes by in situ generation and decomposition of electronically diversified diazo compounds

The modular synthesis of a variety of trans 1,2-disubstituted cyclopropanes in a safe and user-friendly one-pot iron-catalyzed cyclopropanation reaction is described. Easily synthesized N-nosylhydrazones are used as diazo precursors, allowing the in situ generation of electron-rich diazo compounds under mild reaction conditions and their direct participation in the cyclopropanation reaction.

Intermolecular metal-free cyclopropanation of alkenes using tosylhydrazones

We describe the first general method for the metal-free cyclopropanation of alkenes by using N-tosylhydrazones as an in situ source of diazo compounds. This new method works with a wide variety of alkenes (styrene derivatives, dienes, enynes, and electron-deficient alkenes) by using N-tosylhydrazones derived from various ketones or aldehydes (aromatic, aliphatic, enones). The reaction is performed with the use of K2CO3 as a base to form the diazo species and is compatible with a wide array of functional groups. A new procedure for the synthesis of cyclopropanes by the formal cyclopropanation of carbonyl compounds and alkenes is described. This metal-free reaction proceeds through the base-promoted decomposition of tosylhydrazones. There is significant tolerance of the functional groups, enabling cyclopropanation in the presence of functionalities often not compatible with other methodologies.

Olefin cyclopropanation with aryl diazocompounds upon catalysis by a dirhodium(II) complex

A dirhodium(II) complex with N-perfluorooctylsulfonylprolinate ligands is found to catalyze the cyclopropanation of olefins with simple aryl diazomethanes. In contrast to previously reported dirhodium(II) catalysts, the present complex works well not only with very electron-rich olefins such as enol ethers, but also with styrenes. Consequently, the present catalyst allows to prepare functionalized diarylcyclopropanes in moderate yields with good diastereoselectivity for the cis product, whereas the enantioselectivity of the reaction appears negligible.

The nickel and palladium catalyzed stereoselective cross coupling of cyclopropyl nucleophiles with aryl halides

The reaction of 2-phenylcyclopropylzinc chloride with some substituted (het)aryl halides gave the corresponding coupling products with good yields and stereoselectivities under the influence of a catalytic amount of Pd(PPh3)4. Other Ni- and Pd-catalysts were less efficient. Alkyl-substituted cyclopropyl nucleophiles gave lower yields.