17540-19-1

Upstream product

• 2362-61-0 trans-2-Phenylcyclohexanol 
• 22040-54-6 trans-(+/-)-1-Acetoxy-2-phenylcyclohexane 
• 22040-54-6 cis-2-phenyl-cyclohexyl acetate 
• 1521-51-3 rac-3-bromocyclohexene 
• 62-53-3 aniline 
• 110-83-8 cyclohexene 
• 14922-16-8 phenylazo phenyl sulfone 
• 114895-10-2 phenylazoxy phenyl sulphone 
• 591-50-4 iodobenzene 
• 67-56-1 methanol 
• 98-80-6 phenylboronic acid 
• 95617-19-9 ((1S,2R)-2-Iodo-cyclohexyl)-benzene 
• 17763-67-6 Phenyl triflate 
• 789-25-3 HSiPh₃ 

Downstream Products

• 771-98-2 1-Phenylcyclohexene 

Relevant academic research and scientific papers

Efficient functionalization of olefins by arylsilanes catalyzed by palladium anionic complexes

The coupling of organosilanes and different olefins was performed efficiently in the presence of anionic complexes, [CA]2[PdX4] and [CA]2[Pd2X6], where CA?=?imidazolium or pyridinium cation. The reaction proceeds according to a Pd(II)-mediated pathway, and Cu(OAc)2 acts as the re-oxidant of Pd(0) formed during the catalytic process. High product yields were obtained for differently substituted olefins at 80?°C in 4?h. Styrylsilanes reacted in the same conditions giving unsymmetrical 1,3-dienes.

A mild method for eliminating alkyl ethers to alkenes

A method for the conversion of methyl ethers into alkenes is described. In a one-step and mild procedure, both conjugated and isolated cyclic alkenes are accessible in mostly good yields using triflic anhydride in combination with triethylamine. This elimination procedure can also be applied to ethyl and benzyl ethers.

Bidentate hydroxyalkyl NHC ligands for the copper-catalyzed asymmetric allylic substitution of allyl phosphates with grignard reagents

Demonstrating their potential: Bidentate alkoxy NHC ligands have been used in the copper-catalyzed asymmetric allylic alkylation of allyl phosphates with Grignard reagents (see scheme). The method provides access to tertiary and quaternary chiral centers with high regio- and enantioselectivity. The system is also applied to the synthesis of chiral E,E-dienes, a key structural motif prevalent in natural products. Copyright

Achieving vinylic selectivity in Mizoroki-heck reaction of cyclic olefins

In Heck reactions of cyclic olefins, the products usually have aryl groups that end up at the allylic and/or homoallylic position. We herein report new selectivity that adds aryl groups to the vinylic position. Cyclic olefins of various ring size worked well. The desired isomers were produced by palladium-hydride-catalyzed isomerization of the initial products. Thus, a specific catalyst must be used so that it can perform two jobs under one set of reaction conditions. Copyright

Selective heck arylation of cyclohexene with homogeneous and heterogeneous palladium catalysts

Palladium catalysts containing Pd(II) supported on Al2O 3 and alumina-based mixed oxides, Al2O3- ZrO2, Al2O3-CeO2, and Al 2O3-Fe2O3, are very effective in the Heck coupling of iodobenzene with cyclohexene in DMF solution. The best results, up to 81% of monoarylated products with a selectivity to 4-phenylcyclohexene (3) close to 90% were obtained with KOH as a base. The catalytic activity of palladium supported on aluminabased oxides was compared with that of homogeneous precursors, such as Pd(OAc)2 and PdCl 2(PhCN)2, used in [Bu4N]Br as the reaction medium. Under such conditions homogeneous systems were more selective and produced up to 60% of monoarylated products with a selectivity to 3 close to 60%. Copyright

Cobalt-catalyzed regioselective dehydrohalogenation of alkyl halides with dimethylphenylsilylmethylmagnesium chloride

Cobalt-catalyzed reactions of haloalkanes with dimethylphenylsilylmethylmagnesium chloride result in highly regioselective dehydrohalogenation. The reaction does not follow the conventional E2 elimination mechanism but includes β-hydride elimination from the corresponding alkylcobalt intermediate. The interesting reaction mechanism of the cobalt-catalyzed dehydrohalogenation offered unique transformations that are otherwise difficult to attain. Copyright

Oxygen-promoted Pd(II) catalysis for the coupling of organoboron compounds and olefins

(Matrix presented) Reported herein is a mild and efficient Pd(ll) catalysis, leading to the formation of carbon-carbon bonds between a broad spectrum of organoboron compounds and alkenes. Molecular oxygen was employed to reoxidize the resultant Pd(0) species back to Pd(ll) during catalytic cycles. This oxygen protocol promoted the desired Pd(ll) catalysis, whereas it retarded competing Pd(0) catalytic pathways such as Heck or Suzuki couplings.

Hypervalent silane and siloxane derivatives and the use thereof

Hypervalent silane and siloxane reagents (preformed or generated in situ) for transmetalation in palladium catalyzed reactions with derivatives of allylic alcohols, aryl halides, electron-withdrawing aryl bromides, and aryl triflates derived from phenols are disclosed. Also disclosed are methods of preparing glycosyl azides by reaction of an azide with a silyl ester in the presence of a phoshine.

The photochemistry of the 4-cyanobenzoic acid esters of trans- and cis-2-phenylcyclohexanol

Irradiation of trans-2-phenylcyclohexyl 4-cyanobenzoate (4) in methanol results in formation of the 1-phenylcyclohexene and 4-cyanobenzoic acid as the major products. The mechanism proposed for this example of the Norrish Type II-like reaction, normally inefficient for the π,π*state of esters, begins with intramolecular electron transfer in the excited singlet state. The next step, intramolecular proton transfer, is highly exergonic as a result of the increased acidity of the benzylic hydrogen of the radical cation and the increased basicity of the carbonyl oxygen of the radical anion. The final step is cleavage of the 1,4-biradical. This mechanism is proposed on the basis of product studies, absorption spectra, fluorescence spectra, oxidation and reduction potentials, and nanosecond laser flash photolysis spectra. The stereochemical requirements for the process have also been examined using solution NMR, the X-ray structure, and MM3 calculations. The stereoisomer, cis-2-phenylcyclohexyl 4-cyanobenzoate (5), undergoes cis to trans isomerization before photofragmentation. Photolysis of the cis isomer in methanol-OD demonstrated that the cis to trans isomerization occurred by inversion at C1.

Heck reactions in hydrothermal, sub-critical water: Water density as an important reaction variable

Heck coupling reactions of iodobenzene and cyclohexene in sub-critical water illustrate the importance of water density as a reaction variable. Altering the water density from 0.03 to 0.84 g/mL and the reaction pressure from 30 to greater than 213 bar at 225°C changed both product and isomer yields. The multiple physical effects of water density were also explored by the addition of ionic salts. Changing the isothermal state of the liquid water, measurably altered coupling reaction pathways suggesting that changes in solvent-solute interactions can influence transition states favoring some configurations and disfavoring others.