5454-79-5Relevant articles and documents
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Hardy,Wicker
, p. 640 (1958)
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Thermodynamics of diastereomeric transformations of alcohols with different carbon-skeleton structures
Kabo, G. J.,Frenkel, M. L.
, p. 377 - 382 (1983)
The gas-phase equilibria of diastereomers have been investigated in a flow system.The following reactions have been studied: (1), threo to-erythro form of 3-methylpentanol-2; (2), cis-to-trans form of 2-, 3-, and 4-methylcyclohexanol; (3), menthol-to-neomenthol; and (4), borneol-to-isoborneol.The values of ΔHr0 and ΔSr0, for (1) and (2) were calculated from the temperature dependence of the equilibrium constants making use of the least-squares method.The values of ΔGr0 (503 K) for transformations (3) and (4) were also determined.It was shown that the enthalpy changes of the reactions increase in the alcohol series: acyclic-to-cyclic-to-bicyclic and this evidently is accounted for by the decrease of degrees of freedom of internal rotation.The determined dependence can be of a great importance for the development of additive schemes for calculating ΔHf0 for cyclic compounds.
Heterogeneous Hydroxyl-Directed Hydrogenation: Control of Diastereoselectivity through Bimetallic Surface Composition
Shumski, Alexander J.,Swann, William A.,Escorcia, Nicole J.,Li, Christina W.
, p. 6128 - 6134 (2021/05/29)
Directed hydrogenation, in which product selectivity is dictated by the binding of an ancillary directing group on the substrate to the catalyst, is typically catalyzed by homogeneous Rh and Ir complexes. No heterogeneous catalyst has been able to achieve equivalently high directivity due to a lack of control over substrate binding orientation at the catalyst surface. In this work, we demonstrate that Pd-Cu bimetallic nanoparticles with both Pd and Cu atoms distributed across the surface are capable of high conversion and diastereoselectivity in the hydroxyl-directed hydrogenation reaction of terpinen-4-ol. We postulate that the OH directing group adsorbs to the more oxophilic Cu atom while the olefin and hydrogen bind to adjacent Pd atoms, thus enabling selective delivery of hydrogen to the olefin from the same face as the directing group with a 16:1 diastereomeric ratio.
SN2 Reaction of Diarylmethyl Anions at Secondary Alkyl and Cycloalkyl Carbons
Shinohara, Riku,Ogawa, Narihito,Kawashima, Hidehisa,Wada, Kyohei,Saito, Shun,Yamazaki, Takashi,Kobayashi, Yuichi
, p. 1461 - 1478 (2019/01/25)
The substitution reaction of the diethyl allylic and propargylic phosphates with Ar2CH anions was applied to sec-alkyl phosphates to compare reactivity and stereoselectivity. However, the substitution took place on the ethyl carbon of the diethyl phosphate group. We then found that the diphenyl phosphate leaving group ((PhO)2PO2) was suited for the substitution at the sec-alkyl carbon. Enantioenriched diphenyl sec-alkyl phosphates with different substituents (Me, Et, iPr) on the vicinal position underwent the substitution reaction with almost complete inversion (>99% enantiospecificity). The substitution reactions of cyclohexyl phosphates possessing cis or trans substituents (Me and/or tBu) at the C4, C3, and C2 positions of the cyclohexane ring were also studied to observe the difference in reactivity among the cis and trans isomers. A transition-state model with the phosphate leaving group ((PhO)2PO2) in the axial position was proposed to explain the difference. This model was supported by computational calculation of the virtual substitution reaction of the structurally simpler “dimethyl” cyclohexyl phosphates (leaving group = (MeO)2PO2) with MeLi. Furthermore, the calculation unexpectedly indicated higher propensity of (PhO)2PO2 as a leaving reactivity than alkyl phosphate groups such as (MeO)2PO2 and (iPrO)2PO2.
Cobalt-Nanoparticles Catalyzed Efficient and Selective Hydrogenation of Aromatic Hydrocarbons
Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Alshammari, Ahmad S.,Altamimi, Rashid M.,Kreyenschulte, Carsten,Pohl, Marga-Martina,Lund, Henrik,Jagadeesh, Rajenahally V.,Beller, Matthias
, p. 8581 - 8591 (2019/09/12)
The development of inexpensive and practical catalysts for arene hydrogenations is key for future valorizations of this general feedstock. Here, we report the development of cobalt nanoparticles supported on silica as selective and general catalysts for such reactions. The specific nanoparticles were prepared by assembling cobalt-pyromellitic acid-piperazine coordination polymer on commercial silica and subsequent pyrolysis. Applying the optimal nanocatalyst, industrial bulk, substituted, and functionalized arenes as well as polycyclic aromatic hydrocarbons are selectively hydrogenated to obtain cyclohexane-based compounds under industrially viable and scalable conditions. The applicability of this hydrogenation methodology is presented for the storage of H2 in liquid organic hydrogen carriers.
