931-71-5Relevant articles and documents
Polysilane-Immobilized Rh-Pt Bimetallic Nanoparticles as Powerful Arene Hydrogenation Catalysts: Synthesis, Reactions under Batch and Flow Conditions and Reaction Mechanism
Miyamura, Hiroyuki,Suzuki, Aya,Yasukawa, Tomohiro,Kobayashi, Shu
supporting information, p. 11325 - 11334 (2018/09/06)
Hydrogenation of arenes is an important reaction not only for hydrogen storage and transport but also for the synthesis of functional molecules such as pharmaceuticals and biologically active compounds. Here, we describe the development of heterogeneous Rh-Pt bimetallic nanoparticle catalysts for the hydrogenation of arenes with inexpensive polysilane as support. The catalysts could be used in both batch and continuous-flow systems with high performance under mild conditions and showed wide substrate generality. In the continuous-flow system, the product could be obtained by simply passing the substrate and 1 atm H2 through a column packed with the catalyst. Remarkably, much higher catalytic performance was observed in the flow system than in the batch system, and extremely strong durability under continuous-flow conditions was demonstrated (>50 days continuous run; turnover number >3.4 × 105). Furthermore, details of the reaction mechanisms and the origin of different kinetics in batch and flow were studied, and the obtained knowledge was applied to develop completely selective arene hydrogenation of compounds containing two aromatic rings toward the synthesis of an active pharmaceutical ingredient.
Triphenylphosphine reduction of saturated endoperoxides
Erden, Ihsan,Gaertner, Christian,Saeed Azimi
scheme or table, p. 3986 - 3989 (2009/12/05)
(Figure Presented) Triphenylphosphine reduction of saturated endoperoxides derived from 6,6-dimethylfulvene and spiro[2.4]hepta-4,6-diene in the presence of nucleophiles results in the formation of products that mainly stem from deoxygenation followed by carbocation formation. Nucleophilic attack by solvent proceeds by an SN1 like mechanism; allyl shifts and cyclopropylcarbinyl-cyclobutyl rearrangements also occur. With the systems lacking carbocation-stabilizing groups, the deoxygenation step is preceded by attack of H2O at the phosphorus.
Pathways of liquid-phase oxidation of cyclohexanol
Puchkov,Buneeva,Perkel'
, p. 248 - 253 (2007/10/03)
The kinetics of product accumulation in uncatalyzed oxidation of cyclohexanol at 403 K was studied. Along with the compounds originating from oxidation of cyclohexanol at position 1 (cyclohexanone, hydrogen peroxide, 1-hydroxycyclohexyl hydroperoxide), products formed by oxidation of C-H bonds at positions 2-4 were detected: 2-, 3-, and 4-hydroxycyclohexyl hydroperoxides (cis and trans isomers), 1,2-, 1,3-, and 1,4-dihydroxycyclohexanes (cis and trans isomers), 2- and 4-hydroxycyclohexanones, and 2-cyclohexenone.