Mechanism of oxidation of methylbenzenes by palladium(II) in trifluoroacetic acid. One-electron transfer and electrophilic substitution

Kozhevnikov, Ivan V.; Kim, Vladimir I.; Talzi, E. P.; Sidelnikov, V. N.

doi:10.1039/c39850001392

Cited by 15 publications

(6 citation statements)

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“…34,35 The functionalisation of alkanes by palladium acetate (Pd(OAc) 2 ) in trifluoroacetic acid has been shown to involve the formation of palladium(0). [36][37][38][39][40][41] But in contrast to Pd(OAc) 2 we do not observe the formation of palladium black in the stoichiometric reaction of cyclohexane with chelated palladium bis-NHC catalysts in trifluoroacetic acid. 42 We therefore believe that the palladium(II) bis-NHC complex catalysed functionalisation of hydrocarbons does not involve the formation of palladium(0).…”

Section: Introductioncontrasting

confidence: 83%

ortho-Phenylene bridged palladium bis-N-heterocyclic carbene complexes: synthesis, structure and catalysis

et al. 2013

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A series of ortho-phenylene bridged palladium bis-NHC complexes has been synthesized. Complexes with imidazolium and benzimidazolium derived NHCs and methyl-/benzyl-wingtips are reported. Bis(benz)imidazoles with a doubly brominated ortho-phenylene bridge could be obtained by an electrophilic substitution reaction. The structure of the complexes could be confirmed by three solid-state structures. All catalysts have been tested in the catalytic functionalisation of propane. The catalytic activity is highly dependent on the ligand, whereas ligand effects on the regioselectivity (n/iso) are much smaller.

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Section: Introductioncontrasting

confidence: 83%

ortho-Phenylene bridged palladium bis-N-heterocyclic carbene complexes: synthesis, structure and catalysis

et al. 2013

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“…The benzylated products obtained in this study were all known compounds and their physical and analytical data had previously been reported. [16][17][18][19][20][21] Diphenylmethane. MS: 167 (100, M21 + ), 152 (30), 115 (10), 91 (20), 65 (15), 51 (20).…”

Section: Experimental Generalmentioning

confidence: 99%

“…[16][17][18][19][20][21] Diphenylmethane. MS: 167 (100, M21 + ), 152 (30), 115 (10), 91 (20), 65 (15), 51 (20).…”

Section: Experimental Generalmentioning

confidence: 99%

Facile benzylation of aromatics in ionic liquid solvents promoted by TfOH, Sc(OTf)₃, and Yb(OTf)₃·xH₂O; New life for a classic transformation

Sarca

Laali

2006

Green Chem.

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Benzylation of aromatics with PhCH 2 Cl and PhCH 2 OH is conveniently performed in [BMIM][OTf] or [BMIM][PF 6 ] ionic liquids (ILs), by using TfOH, Sc(OTf) 3 and Yb(OTf) 3 ?xH 2 O as catalysts. With PhCH 2 Cl, high conversions were achieved by using 20% Sc(OTf) 3 or Yb(OTf) 3 hydrate under mild conditions (65-80 uC). Triflic acid is superior to Yb(OTf) 3 as promoter for benzylation with PhCH 2 OH in the IL solvent, since in most cases little or no dibenzyl ether (DBE) was formed as side product. The scope of arene benzylation with benzyl alcohol in the TfOHcatalyzed and Yb(OTf) 3 -catalyzed reactions was examined in [BMIM][PF 6 ] solvent. Whereas conversions are typically quantitative at 65-70 uC, minor amounts of DBE were produced, along with the corresponding ArCH 2 Ph (with minor amounts of dibenzylated derivatives being detected in benzylation of mesitylene and biphenyl). Substrate selectivity (K T /K B ) and regioselectivity (isomer distribution) measured for benzylation in IL solvents employing TfOH or Yb(OTf) 3 as catalyst are similar to those reported previously in molecular solvents employing Nafion-H, AlCl 3 , TiCl 4 or ''clayzic''. The observed high yields and chemoselectivities (absence of DBE), coupled to easy isolation of the benzylated products and recycling/reuse of the IL, provide a new life for this classical transformation.

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“…Kozhevnikov et al reported the oxidative homo-coupling of pxylene using Pd via a one electron transfer mechanism [34]. We have chosen p-xylene as a model substrate to form 2,2 0 ,5,5 0 -tetramethylbiphenyl using PhI(OAc) 2 as the oxidant (Table 1).…”

Section: Introductionmentioning

confidence: 99%

Gold-catalyzed direct oxidative coupling reactions of non-activated arenes

Kar

Mangu

Kaiser

et al. 2009

Journal of Organometallic Chemistry

103

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Mechanism of oxidation of methylbenzenes by palladium(II) in trifluoroacetic acid. One-electron transfer and electrophilic substitution

Cited by 15 publications

References 1 publication

ortho-Phenylene bridged palladium bis-N-heterocyclic carbene complexes: synthesis, structure and catalysis

ortho-Phenylene bridged palladium bis-N-heterocyclic carbene complexes: synthesis, structure and catalysis

Facile benzylation of aromatics in ionic liquid solvents promoted by TfOH, Sc(OTf)₃, and Yb(OTf)₃·xH₂O; New life for a classic transformation

Gold-catalyzed direct oxidative coupling reactions of non-activated arenes

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Mechanism of oxidation of methylbenzenes by palladium(II) in trifluoroacetic acid. One-electron transfer and electrophilic substitution

Cited by 15 publications

References 1 publication

ortho-Phenylene bridged palladium bis-N-heterocyclic carbene complexes: synthesis, structure and catalysis

ortho-Phenylene bridged palladium bis-N-heterocyclic carbene complexes: synthesis, structure and catalysis

Facile benzylation of aromatics in ionic liquid solvents promoted by TfOH, Sc(OTf)3, and Yb(OTf)3·xH2O; New life for a classic transformation

Gold-catalyzed direct oxidative coupling reactions of non-activated arenes

Contact Info

Product

Resources

About

Facile benzylation of aromatics in ionic liquid solvents promoted by TfOH, Sc(OTf)₃, and Yb(OTf)₃·xH₂O; New life for a classic transformation