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Upstream product

• 1765-40-8 (bromomethyl)pentafluorobenzene 
• 137676-33-6 2,3,4,5,6-Pentafluorobenzyl Methyl Sulphoxide 
• 108-88-3 toluene 
• 778-34-7 1,2,3,4,5-pentafluoro-6-(trichloromethyl)benzene 
• 392-56-3 Hexafluorobenzene 
• 5267-59-4 2,4,5-Tris-pentafluorophenyl-[1,3]dioxolane 
• 653-21-4 2,3,4,5,6-pentafluorophenylacetic acid 
• 653-37-2 perfluorobenzaldehyde 
• 100-52-7 benzaldehyde 
• 1373139-21-9 C₉H₅F₅O₃ 
• 1736-60-3 1-allyl-2,3,4,5,6-pentafluorobenzene 
• 771-56-2 2,3,4,5,6-pentafluorotoluene 
• 440-60-8 (2,3,4,5,6-pentafluorophenyl)methanol 
• 653-35-0 2,3,4,5,6-pentafluorobenzyl chloride 

Relevant academic research and scientific papers

Photochemical Reductive C–C Coupling with a Guanidine Electron Donor

The metal-free photoinduced reductive C–C coupling reactions of a number of substituted benzyl halides (15 examples) with the organic electron-donor 2,3,5,6-tetrakis(tetramethylguanidino)pyridine are evaluated. Depending on the substituents at the benzyl group, a C–C coupling product yield in the range 50–95 % is achieved. The photochemical benzyl-radical formation by homolytic N–C bond cleavage of the initially formed benzyl-pyridinium salts is the rate-determining step of these reactions. Electron-withdrawing as well as -donating substituents at the phenyl group increase the reaction rate. Quantum chemical computations did not reveal any correlation between either the enthalpy or Gibbs free energy of the N–C bond cleavage step and the experimentally determined first-order rate constants. Instead, the structural difference between the excited state generated by irradiation and the electronic ground state of the pyridinium ions could be used to rationalize the differences in the reaction rates.

A well-defined low-valent cobalt catalyst Co(PMe3)4 with dimethylzinc: a simple catalytic approach for the reductive dimerization of benzyl halides

Herein, we report the first catalytic version of a cobalt-catalysed reductive homocoupling of benzyl halides which proceeds with low catalyst loadings (0.5 to 5 mol%). By synthetizing each cobalt intermediate we demonstrate that reaction proceeds through two single electron transfers (SET) and that dimethylzinc is only involved in the regeneration of the catalytic species.

A clean and selective radical homocoupling employing carboxylic acids with titania photoredox catalysis

A titania photoredox catalysis protocol was developed for the homocoupling of C-centered radicals derived from carboxylic acids. Intermolecular reactions were generally efficient and selective, furnishing the desired dimers in good yields under mild neutral conditions. Selective cross-coupling with two acids proved unsuccessful. An intra-molecular adaptation enabled macrocycles to be prepared, albeit in modest yields. (Chemical Equation Presented).

Csp3-Csp3 homocoupling reaction of benzyl halides catalyzed by rhodium

A highly reactive alkylrhodium complex was formed from Me2Zn and RhCl(PPh3)3 and effectively catalyzed a Csp 3-Csp3 homocoupling reaction of benzyl halides. A Csp 3-Csp3 coupling reaction using Rh catalyst has not been reported up to now. The reaction proceeded under very mild conditions and gave the corresponding homocoupling products even if they had reactive substituents such as an uncovered formyl or hydroxymethyl group.

Ti-catalyzed homolytic opening of ozonides: A sustainable C-C bond-forming reaction

The unprecedented homolytic opening of ozonides promoted and catalyzed by titanocene(III) is reported. This novel reaction proceeds at room temperature under neutral, mild conditions compatible with many functional groups and provides carbon radicals suitable to form C-C bonds via both homocoupling and cross-coupling processes. The procedure has been advantageously exploited for the straightforward synthesis of the natural product brittonin A.

Benzyl bromide addition to pentafluorobenzaldehyde by Zaitsev-Barbier reaction promoted with complex systems underlain by iron pentacarbonyl

Iron pentacarbonyl promots addition of benzyl bromide to benzaldehydes by Zaitsev-Barbier reaction only in the presence of nucleophilic additives [HMPT or (S)-N-benzoyl-2-methoxycarbonylpyrrolidine].

Kolbe carbon-carbon coupling electrosynthesis using solid-supported bases

(Chemical Equation Presented) We have developed a novel electrolytic system for Kolbe carbon-carbon coupling electrosynthesis based on the acid-base reaction between carboxylic acids as a substrate and solid-supported bases. On the basis of the electrolytic system, Kolbe electrolysis of various carboxylic acids was successfully carried out to provide the corresponding homocoupling products in moderate to excellent yields.

Flash vacuum pyrolysis over magnesium. Part 1 - Pyrolysis of benzylic, other aryl/alkyl and aliphatic halides

Flash vacuum pyrolysis over a bed of freshly sublimed magnesium on glass wool results in efficient coupling of benzyl halides to give the corresponding bibenzyls. Where an ortho halogen substituent is present further dehalogenation gives some dihydroanthracene and anthracene. Efficient coupling is also observed for halomethylnaphthalenes and halodiphenylmethanes while chlorotriphenylmethane gives 4,4′-bis(diphenylmethyl)biphenyl. By using α,α′-dihalo-o-xylenes, benzocyclobutenes are obtained in good yield, while the isomeric α,α′-dihalo-p-xylenes give a range of high thermal stability polymers by polymerisation of the initially formed p-xylylenes. Other haloalkylbenzenes undergo largely dehydrohalogenation where this is possible, in some cases resulting in cyclisation. Deoxygenation is also observed with haloalkyl phenyl ketones to give phenylalkynes as well as other products. With simple alkyl halides there is efficient elimination of HCl or HBr to give alkenes. For aliphatic dihalides this also occurs to give dienes but there is also cyclisation to give cycloalkanes and dehalogenation with hydrogen atom transfer to give alkenes in some cases. For 5-bromopent-1-ene the products are those expected from a radical pathway but for 6-bromohex-1-ene they are clearly not. For 2,2-dichloropropane and 1,1-dichloropropane elimination of HCl occurs but for 1,1-dichlorobutane, -pentane and -hexane partial hydrolysis followed by elimination of HCl gives E, E-, E,Z- and Z,Z- isomers of the dialk-1-enyl ethers and fully assigned 13C NMR data are presented for these. With 6-chlorohex-1-yne and 7-chlorohept-1-yne there is cyclisation to give methylenecycloalkanes and -cycloalkynes. The behaviour of 1,2-dibromocyclohexane and 1,2-dichlorocyclooctane under these conditions is also examined. Various pieces of evidence are presented that suggest that these processes do not involve generation of free gas-phase radicals but rather surface-adsorbed organometallic species.

Reductive transformations of organofluorine compounds: II. Hydrodechlorination of chloropolyfluoroarenes by the action of zinc

Polyfluoroarenes containing chlorine atoms in the aromatic ring and/or in the benzylic position undergo hydrodechlorination by the action of zinc in aqueous dimethylformamide. The use of Zn/Cu and addition of salts (NaCl, Na2SO4, NH4Cl) favor reductive dechlorination of the Carom - Cl bond. Polyfluorobenzotrichlorides react with excess zinc to give the corresponding CH3-substituted derivatives, otherwise CH2Cl- and CHCl2-containing compounds are formed. The reduction of C6F5CCl3 and C6F5CH2Cl with zinc in the presence of copper provides lower yields of the hydrodechlorination products and leads to formation of 1,2-bis(pentafluorophenyl)ethane.

Chemistry of bis(pentafluorobenzyl) phosphines and phosphine oxides. Single-crystal X-ray diffraction study of η6-mesitylene-dichloro-[bis(pentafluorobenzyl)phosphinous acid]-ruthenium(II) and of 1,2-bis(pentafluorophenyl)ethane

The reaction of pentafluorobenzyl magnesium bromide with phosphorus trichloride in a 2:1 molar ratio led to the disubstituted product, bis(pentafluorobenzyl)bromophosphine 1, which, upon reaction with lithium aluminium hydride, was converted to bis-(penta