64847-85-4

Upstream product

• 930-68-7 cyclohexenone 
• 925-90-6 ethylmagnesium bromide 
• 17299-34-2 3-ethylcyclohex-2-en-1-one 
• 10467-10-4 ethylmagnesium iodide 
• 97-94-9 triethyl borane 
• 75-77-4 chloro-trimethyl-silane 
• 557-18-6 diethylmagnesium 
• 811-49-4 ethyllithium 
• 557-20-0 diethylzinc 
• 10568-38-4 3-ethylanisole 
• 58237-58-4 1-Diazooctan-2-one 
• 1004-58-6 1,4-dioxa-spiro[4.5]dec-6-ene 
• 2386-64-3 ethylmagnesium chloride 
• 97-93-8 triethylaluminum 

Downstream Products

• 28122-24-9 (3-ethylphenyl)phenylmethane 
• 59671-57-7 1-(5-Ethyl-cyclohex-1-enyl)-3,3-dimethyl-butan-2-one 
• 22461-89-8 (R)-3-ethylcyclohexanone 
• 22461-89-8 3-ethylcyclohexanone 
• 935-57-9 3-Aethyl-cyclohexanon-cyanhydrin 
• 307317-68-6 methyl 4-ethyl-2-oxocyclohexanecarboxylate 
• 1256267-75-0 (S,R,R)-N-((2-ethyl-6-oxocyclohexyl)(phenyl)methyl)-4-methylbenzenesulfonamide 
• 1256267-76-1 (R,R,R)-N-((2-ethyl-6-oxocyclohexyl)(phenyl)methyl)-4-methylbenzenesulfonamide 
• 87759-25-9 (1S,3R)-3-ethyl-cyclohexanol 

Relevant academic research and scientific papers

Deciphering Reactivity and Selectivity Patterns in Aliphatic C-H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives

A kinetic, product, and computational study on the reactions of the cumyloxyl radical with monosubstituted cyclopentanes and cyclohexanes has been carried out. HAT rates, site-selectivities for C-H bond oxidation, and DFT computations provide quantitative information and theoretical models to explain the observed patterns. Cyclopentanes functionalize predominantly at C-1, and tertiary C-H bond activation barriers decrease on going from methyl- and tert-butylcyclopentane to phenylcyclopentane, in line with the computed C-H BDEs. With cyclohexanes, the relative importance of HAT from C-1 decreases on going from methyl- and phenylcyclohexane to ethyl-, isopropyl-, and tert-butylcyclohexane. Deactivation is also observed at C-2 with site-selectivity that progressively shifts to C-3 and C-4 with increasing substituent steric bulk. The site-selectivities observed in the corresponding oxidations promoted by ethyl(trifluoromethyl)dioxirane support this mechanistic picture. Comparison of these results with those obtained previously for C-H bond azidation and functionalizations promoted by the PINO radical of phenyl and tert-butylcyclohexane, together with new calculations, provides a mechanistic framework for understanding C-H bond functionalization of cycloalkanes. The nature of the HAT reagent, C-H bond strengths, and torsional effects are important determinants of site-selectivity, with the latter effects that play a major role in the reactions of oxygen-centered HAT reagents with monosubstituted cyclohexanes.

Counterion Enhanced Organocatalysis: A Novel Approach for the Asymmetric Transfer Hydrogenation of Enones

We present a novel strategy for organocatalytic transfer hydrogenations relying on an ion-paired catalyst of natural l-amino acids as main source of chirality in combination with racemic, atropisomeric phosphoric acids as counteranion. The combination of a chiral cation with a structurally flexible anion resulted in a novel chiral framework for asymmetric transfer hydrogenations with enhanced selectivity through synergistic effects. The optimized catalytic system, in combination with a Hantzsch ester as hydrogen source for biomimetic transfer hydrogenation, enabled high enantioselectivity and excellent yields for a series of α,β-unsaturated cyclohexenones under mild conditions. Moreover, owing to the use of readily available and chiral pool-derived building blocks, it could be prepared in a straightforward and significantly cheaper way compared to the current state of the art.

Mechanistic-Insight-Driven Rate Enhancement of Asymmetric Copper-Catalyzed 1,4-Addition of Dialkylzinc Reagents to Enones

The combination of [Cu(MeCN)4]TFA·TFAH (TFA = O2CCF3) with Feringa's phosphoramidite ligand (LA) provides an exceptionally active (0.75 mol %) catalyst for asymmetric conjugate additions of ZnR2 (R = Et and Me at -40 to -80 °C) to enones. Kinetic and other studies of the addition of ZnEt2 to cyclohex-2-en-1-one indicate a transition state stoichiometry composition of (ZnEt2)3(enone)4Cu2(LA)3 that is generated by transmetalation from Et2Zn(enone)2. Catalyst genesis is significantly slower than turnover (which has limited previous attempts to attain useful kinetic data); in the initial stages, varying populations of catalytically inactive, off-cycle, species are present. These issues are overcome by a double-dose kinetic analysis protocol. A rest state of [LACu(Et)(μ-TFA)(μ-{(enone)(ZnEt)2(enolate)})CuLA2]+ (through the equivalence of enolate = enone + ZnEt2) is supported by DFT studies (ωB97X-D/SRSC). Rate-determining ZnEt2(enone)2 transmetalation drives the exceptionally high catalytic activity of this system.

Enantioselective Cu-catalyzed 1,4-additions of organozinc and Grignard reagents to enones: Exceptional performance of the hydrido-phosphite-ligand BIFOP-H

Enantioselective Cu(I),(II)-(i.e. CuCl, CuCl2, Cu(OTf)2)-catalyzed 1,4-additions of organozinc, i.e. (Et, Me)2Zn, and Grignard reagents, i.e. (Et, Me)MgBr, to chalcone, cyclohexenone and chromone are studied, employing fencholate-based phosphorus ligands, e.g. biphenyl-2,2′-bisfenchyl hydrido phosphite = BIFOP-H. The CuCl·BIFOP-H-catalyzed 1,4-addition of Et2Zn to chalcone yields up to 93% and 99% ee, exceeding established BINOL- and TADDOL-based phosphoramidite ligands. Remarkably, CuCl performs better in 1,4-additions to chalcone (CuCl: 76% ee; Cu(OTf)2: 49% ee; CuCl2: 42% ee) while Cu(OTf)2 performs better in 1,4-additions to cyclohexenone (Cu(OTf)2: 65% ee; CuCl: 20% ee). The computation of the reaction pathway is done for the CuI-catalyzed 1,4-addition to chalcone (CuII will be in situ reduced to CuI by a reagent, TPSS-D3(BJ)/def2-TZVP//B3LYP-D3(BJ)/def2-SVP) for six different model ligands, i.e. (MeO)2P-X (X = H, F, Me, OMe, NMe2 and PMe3). Origins of enantioselectivities are analyzed (M06-2X-D3/def2-TZVP//B3LYP-D3(BJ)/def2-SVP) for transition structures of the 1,4-methylation of chalcone with the Cu·BIFOP-H catalyst and explain the experimentally observed (R)-enantiomer's preference.

Enantiopure sulfoximines-catalyzed 1, 4-additions to 2-en-ketone

An efficient chiral catalyst procedure for the preparation of β-chiral ketone via the 1, 4-additions reaction of 2-en-ketone has been developed using enantiopure sulfoximines modified with functional groups as ligands. The carefully design and synthesized

CuI-Catalysed Enantioselective Alkyl 1,4-Additions to (E)-Nitroalkenes and Cyclic Enones with Phosphino-Oxazoline Ligands

Catalytic enantioselective conjugate additions of simple alkyl groups to nitroalkenes or cyclic enones that result in the formation of tertiary C–C bonds are described. For these stereoselective addition reactions, new chiral phosphino-oxazoline ligands w

Ductile Pd-Catalysed Hydrodearomatization of Phenol-Containing Bio-Oils Into Either Ketones or Alcohols using PMHS and H2O as Hydrogen Source

A series of phenolic bio-oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and water as reducing agent. The selectivity of the reaction was governed by the water concentration where selectivity to alcohol was favoured at higher water concentrations. As phenolic bio-oil examples cardanol and beech wood tar creosote were studied as substrate to the developed reaction conditions. Cardanol was hydrodearomatized into 3-pentadecylcyclohexanone in excellent yield. From beech wood tar creosote, a mixture of cyclohexanols was produced. No hydrodeoxygenation occurred, suggesting the applicability of the reported method for the production of ketone-alcohol oil from biomass. (Figure presented.).

Inversions in asymmetric conjugate addition reaction of cyclic enones catalyzed by the Cu/NHC-AgX system: Factors affecting the stereoselective formation of both enantiomers

A switchable enantioselectivity was achieved in a Cu-catalyzed asymmetric conjugate addition (ACA) reaction. The ethylene-bridged, hydroxyamide-functionalized NHC-AgI complex, readily accessible from a chiral β-amino alcohol, was found to be a versatile c

The Cu-catalyzed asymmetric conjugate addition with chiral diphosphite ligands derived from D-(-)-tartaric acid

A series of diphosphite ligands, which were derived from D-(-)-tartaric acid, have been synthesized and successfully applied in the Cu-catalyzed asymmetric conjugate addition of organozincs to enones. There was a synergic effect between the stereogenic ce

Novel MOP-type H8-binaphthyl monodentate phosphite ligands and their applications in transition metal-catalyzed asymmetric 1,4-conjugate additions and hydroformylations

A new series of monodentate phosphites based on the rigid, axially chiral monoesterified H8-BINOL, which are easy to prepare from the readily accessible phosphorylating reagents (Sa)- or (Ra)-1,1′-binaphthyl-2,2′-diylchlorophosphite and (Sa)- or (Ra)-1,1′-H8-binaphthyl-2,2′-diylchlorophosphite, have been synthesized. All ligands were purified on a silica gel column under a nitrogen atmosphere with moderate yields, and were white solids and air-stable at room temperature. These ligands afforded good to excellent enantioselectivities in the Cu-catalyzed 1,4-conjugate addition of 2-cyclohexenone with nucleophiles Et2Zn (96% ee) and with Ph2Zn (65% ee), 2-cyclopentenone with Et2Zn (95% ee), 2-cycloheptenone with Et2Zn (76% ee), and 5,6-dihydro-2H-pyran-2-one with Et2Zn (90% ee). In the Rh-catalyzed asymmetric hydroformylation of styrene, these ligands showed a chemoselectivity of >99% in aldehydes, and a satisfactory branched over linear ratio (96/4). Moreover, the sense of the enantiodiscrimination of the products was mainly determined by the configuration of the BINOL-based or H8-BINOL-based phosphocycle.