937-05-3Relevant articles and documents
Joris et al.
, p. 4759 (1968)
Reaction of Trialkylboranes with Sodium Diethyldihydroaluminate in the Presence of 1,4-Diazabicyclooctane. A Convenient, General Method for Preparation of Sodium Trialkylborohydrides
Hubbard, John L.,Fuller, Joseph C.,Jackson, Thomas C.,Singaram, Bakthan
, p. 8311 - 8316 (1993)
Trialkylboranes in tetrahydrofuran (THF) or diethyl ether (EE) solutions, including those with exceptionally large steric requirements, react readily with toluene solutions of sodium diethyldihydroaluminate in the presence of 1,4-diazabicyclooctane (DABCO) to yield the corresponding sodium trialkylborohydrides and diethylaluminum hydride.The diethylaluminum hydride precipitates from solution as its DABCO adduct, with the use of EE as solvent facilitating the separation.This reaction constitutes a convenient, general method for preparing sodium trialkylborohydrides.
Diastereoselectivity in gas-phase hydride reduction reactions of ketones
Artau, Alexander,Ho, Yeunghaw,Kenttaemaa, Hilkka,Squires, Robert R.
, p. 7130 - 7137 (1999)
The intrinsic diastereoselectivity of the reduction of a series of cyclic ketones by pentacoordinate silicon hydride ions was investigated in the gas phase with the use of the flowing afterglow-triple quadrupole technique. The percent axial reduction of 4-tert-butylcyclohexanone (1), 2-methylcyclohexanone (2), 3,3,5-trimethylcyclohexanone (3), norcamphor (4), 2-tert-butyl-1,3-dioxan-5-one (5), and 2-tert-butyl-1,3-dithian-5-one (6) was determined by collision-induced dissociation experiments. The results show that axial (exo) reduction dominates for 1, 2, and 4, whereas equatorial reduction is dominant for 3, 5, and 6. The trend observed for the reduction diastereoselectivity of compounds 1-4 and 6 matches their condensed-phase behavior; i.e., the percent axial reduction is reduced when steric hindrance of the ketones is increased (1, 99 ± 3%; 2, 68 ± 5; 3, 9 ± 3%). The remarkable consistency of the results obtained in the gas phase and in solution suggests that environmental effects are either unimportant or cancel out and that the reduction diastereoselectivity is a property that can be attributed to the intrinsic nature of the isolated reactants. Qualitatively, the predictions made by Houk et al. regarding the diastereoselectivity of the reduction of 5 and 6 in the gas phase were confirmed, i.e., a preferred equatorial approach of the hydride reducing agent. The preference of compound 5 to undergo equatorial reduction in the gas phase (33 ± 4% axial reduction) contrasts with the almost exclusive. axial reduction reported in solution (93%). This deviation is likely caused by the strong electrostatic repulsion between the nucleophilic hydride reagent and the ring heteroatoms in 5. Compound 6 exhibits an even stronger preference for equatorial reduction (16 ± 4% axial reduction), in agreement with experimental results obtained by others in the condensed phase. Earlier calculations predict an even stronger preference for equatorial reduction. These results are readily rationalized in terms of competition among steric, torsional, and electrostatic effects.
Trans-Selective and Switchable Arene Hydrogenation of Phenol Derivatives
Bergander, Klaus,Glorius, Frank,Heusler, Arne,Wollenburg, Marco
, p. 11365 - 11370 (2020/11/24)
A trans-selective arene hydrogenation of abundant phenol derivatives catalyzed by a commercially available heterogeneous palladium catalyst is reported. The described method tolerates a variety of functional groups and provides access to a broad scope of trans-configurated cyclohexanols as potential building blocks for life sciences and beyond in a one-step procedure. The transformation is strategically important because arene hydrogenation preferentially delivers the opposite cis-isomers. The diastereoselectivity of the phenol hydrogenation can be switched to the cis-isomers by employing rhodium-based catalysts. Moreover, a protocol for the chemoselective hydrogenation of phenols to cyclohexanones was developed.
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.
