38706-73-9Relevant academic research and scientific papers
Selective hydrogenation of fluorinated arenes using rhodium nanoparticles on molecularly modified silica
Bordet, Alexis,Emondts, Meike,Kacem, Souha,Leitner, Walter
, p. 8120 - 8126 (2020/12/28)
The production of fluorinated cyclohexane derivatives is accomplished through the selective hydrogenation of readily available fluorinated arenes using Rh nanoparticles on molecularly modified silica supports (Rh?Si-R) as highly effective and recyclable catalysts. The catalyst preparation comprises grafting non-polar molecular entities on the SiO2 surface generating a hydrophobic environment for controlled deposition of well-defined rhodium particles from a simple organometallic precursor. A broad range of fluorinated cyclohexane derivatives was shown to be accessible with excellent efficacy (0.05-0.5 mol% Rh, 10-55 bar H2, 80-100 °C, 1-2 h), including industrially relevant building blocks. Addition of CaO as scavenger for trace amounts of HF greatly improves the recyclability of the catalytic system and prevents the risks associated to the presence of HF, without compromising the activity and selectivity of the reaction.
Hydrogenation of fluoroarenes: Direct access to all-cis-(multi)fluorinated cycloalkanes
Wiesenfeldt, Mario P.,Nairoukh, Zackaria,Li, Wei,Glorius, Frank
, (2017/09/23)
All-cis-multifluorinated cycloalkanes exhibit intriguing electronic properties. In particular, they display extremely high dipole moments perpendicular to the aliphatic ring, making them highly desired motifs in material science. Very few such motifs have been prepared, as their syntheses require multistep sequences from diastereoselectively prefunctionalized precursors. Herein we report a synthetic strategy to access these valuable materials via the rhodium-cyclic (alkyl)(amino)carbene (CAAC)-catalyzed hydrogenation of readily available fluorinated arenes in hexane. This route enables the scalable single-step preparation of an abundance of multisubstituted and multifluorinated cycloalkanes, including all-cis-1, 2, 3, 4, 5, 6-hexafluorocyclohexane as well as cis-configured fluorinated aliphatic heterocycles.
Mechanistic aspects of the fluorination of cyclohexane and cyclohexene with acetyl hypofluorite in acetic acid
Visser, G. W. M.,Bakker, C. N. M.,Halteren, R. W. v.,Herscheld, J. D. M.,Brinkman, G. A.,Hoekstra, A.
, p. 214 - 219 (2007/10/02)
The reaction of acetyl hypofluorite in acetic acid with both cyclohexane and cyclohexene has been investigated.Analysis by GCMS and radio-HPLC, using (18)F as a tracer, revealed that apart from typical products expected from a radical reaction, several compounds originating from carbocationic intermediates were formed.On the basis of the observed products, a single-electrontransfer (SET) mechanism leading to an intermediate radical-cation is proposed.
