7484-19-7

Upstream product

• 2251-50-5 pentafluorobenzoylchloride 
• 100-44-7 benzyl chloride 
• 434-64-0 perfluorotoluene 
• 71-43-2 benzene 
• 6485-79-6 chlorotriisopropylsilane 
• 617-86-7 triethylsilane 
• 1438-82-0 1,1,1,3,3-pentamethyl-1,3-disiloxane 
• 392-56-3 Hexafluorobenzene 
• 5281-18-5 benzaldehyde, hydrazone 
• 100-52-7 benzaldehyde 
• 1536-23-8 2,3,4,5,6-pentafluorobenzophenone 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 363-72-4 Pentafluorobenzene 
• 1666-17-7 benzaldehyde p-toluenesulfonylhydrazone 

Relevant academic research and scientific papers

Synthesis of low-valent uranium fluorides by C-F bond activation

The uranium(iii) alkyl, Tp2UCH2Ph (Tp = hydrotris(3,5-dimethylpyrazolyl)borate), activates C-F bonds on a variety of fluorinated substrates. From these reactions two new uranium containing products, Tp2UF and Tp2UF2, were isolated and characterized by 1H, 13C, 11B NMR, infrared and electronic absorption spectroscopies, as well as X-ray crystallography. Formation of the uranium(III) or uranium(iv) product was found to be substrate dependent.

+: A Masked Potent Boron Lewis Acid

The chemistry of the boron cation has been revitalized in the past decade due to its newfound application in stoichiometric and catalytic organic reactions. To extend the frontier of boron cation catalysis, we came to discover that a mesityl-substituted η5-Cp*-coordinated boron cation could serve as a powerful Lewis acid for organic catalytic transformations. The boron cation [Cp*B-Mes][B(C6F5)4] ([1][B(C6F5)4]) stabilized in a boronium-like electronic structure binds to Et3PO readily and displays an acceptor number exceeding that of B(C6F5)3 on the Gutmann-Beckett acidity scale. The steric and electronic stabilization exerted by the electron-donating Cp? renders the highly Lewis acidic boron cation an easy-to-handle catalyst for hydrodeoxygenation of aryl ketones at ambient temperature. The exceptional catalytic performance of [1]+ implies that the incorporation of a coordinatively flexible substituent at boron is critical in bringing catalytic activity and stability to boron cation catalysts.

Umpolung cross-coupling of polyfluoroarenes with hydrazones: Via activation of C-F bonds

An umpolung strategy for the cross-coupling of polyfluoroarenes with various substituted hydrazones to construct C(sp2)-C(sp3) bonds is developed. In this strategy, the C-F bond of polyfluoroarenes is cleaved and coupled with moisture- and air-stable hydrazones under mild conditions with good to excellent yields. This method provides a useful tool for synthesizing polyfluorinated pharmaceuticals and functional materials.

Kinetic hydricity of silane hydrides in the gas phase

Herein, gas phase studies of the kinetic hydricity of a series of silane hydrides are described. An understanding of hydricity is important as hydride reactions figure largely in many processes, including organic synthesis, photoelectrocatalysis, and hydrogen activation. We find that hydricity trends in the gas phase differ from those in solution, revealing the effect of solvent. Calculations and further experiments, including H/D studies, were used to delve into the reactivity and structure of the reactants. These studies also represent a first step toward systematically understanding nucleophilicity and electrophilicity in the absence of solvent.

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.

Palladium-Catalyzed Decarboxylation of Benzyl Fluorobenzoates

The decarboxylation of benzyl fluorobenzoates has been developed by using the palladium catalyst prepared in situ from Pd(η 3 -allyl)Cp and bulky monophosphine ligand XPhos. The catalytic reaction afforded a range of fluorinated diarylmethanes in good yields with broad functional-group compatibility. The substrates were readily synthesized by condensation of the corresponding benzoic acid with benzyl alcohol. Therefore, the transformation is formally regarded as a cross-coupling reaction between fluorine-containing benzoic acids and benzyl alcohols.

Catalytic Friedel–Crafts Reactions of Highly Electronically Deactivated Benzylic Alcohols

Highly electronically deactivated benzylic alcohols, including those with a CF3 group adjacent to the OH-bearing carbon, undergo dehydrative Friedel–Crafts reactions upon exposure to catalytic Br?nsted acid in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) solvent. Titration and kinetic experiments support the involvement of higher order solvent/acid clusters in catalysis.

Use of Trifluoromethyl Groups for Catalytic Benzylation and Alkylation with Subsequent Hydrodefluorination

The electrophilic organofluorophosphonium catalyst [(C6F5)3PF][B(C6F5)4] is shown to effect benzylation or alkylation by aryl and alkyl CF3 groups with subsequent hydrodefluorination, thus resulting in a net transformation of CF3 into CH2-aryl fragments. In the case of alkyl CF3 groups, Friedel-Crafts alkylation by the difluorocarbocation proceeded without cation rearrangement, in contrast to the corresponding reactions of alkyl monofluorides.

Copper(I)-Catalyzed Alkylation of Polyfluoroarenes through Direct C - H Bond Functionalization

The copper(I)-catalyzed alkylation of electron-deficient polyfluoroarenes with N-tosylhydrazones and diazo compounds has been developed. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of C(sp2) - C(sp3) bonds with polyfluoroarenes through direct C - H bond functionalization. Mechanistically, copper(I) carbene formation and subsequent migratory insertion are proposed as the key steps in the reaction pathway.

A cooperative Pd-Cu system for direct C-H bond arylation

A novel and efficient method for C-H arylation using well-defined Pd- and Cu-NHC systems has been developed. This process promotes the challenging construction of C-C bonds from arenes or heteroarenes using aryl bromides and chlorides. Mechanistic studies