4714-09-4

Upstream product

• 945-49-3 cyclohexylphenylmethanol 
• 144-62-7 oxalic acid 
• 89002-92-6 1-benzylcyclohex-2-enyl p-tolyl sulphone 
• 89003-02-1 3-benzylcyclohex-2-enyl p-tolyl sulphone 
• 100-39-0 benzyl bromide 
• 87413-32-9 (cyclohex-2-enylsulfonyl)benzene 
• 1944-01-0 1-benzylcyclohexan-1-ol 
• 100-51-6 benzyl alcohol 
• 110-83-8 cyclohexene 
• 28075-50-5 cyclohex-1-en-1-yl trifluoromethane sulfonate 
• 2044-08-8 1-bromocyclohex-1-ene 
• 1589-82-8 phenylmagnesium bromide 
• 108-94-1 cyclohexanone 
• 6921-34-2 benzylmagnesium chloride 

Downstream Products

• 7583-78-0 1-benzyl-1,2-epoxycyclohexane 
• 861316-23-6 1-benzylcyclohexane-1,2-diol 
• 861315-74-4 1,2-dibromo-1-benzyl-cyclohexane 
• 861316-39-4 1-benzyl-2-iodo-cyclohexanol 
• 861008-61-9 4-Hydroxy-1-(1-benzyl-cyclohexyl)-benzol 
• 65-85-0 benzoic acid 
• 13694-34-3 2-Benzyl-3-hydroperoxycyclohexen-⁽¹⁾ 
• 5333-61-9 2-benzylcyclohexan-1-ol 
• 1135-72-4 1-(hydroxy(phenyl)methyl)cyclohexan-1-ol 
• 13694-42-3 (+/-)-cylohexylphenylmethyl hydroperoxide 
• 946-33-8 2-benzylcyclohexan-1-one 
• 50648-70-9 trans-2-benzylidenecyclohexanol 
• 81523-04-8 1-benzyl-trans-2-methoxy-r-1-cyclohexanol 
• 34492-10-9 1-benzyl-r-1,t-2-cyclohexane-1,2-diol 

Relevant academic research and scientific papers

Triphosgene and DMAP as Mild Reagents for Chemoselective Dehydration of Tertiary Alcohols

The utility of triphosgene and DMAP as mild reagents for chemoselective dehydration of tertiary alcohols is reported. Performed in dichloromethane at room temperature, this reaction is readily tolerated by a broad scope of substrates, yielding alkenes preferentially with the (E)-geometry. While formation of the Hofmann products is generally favored, a dramatic change in alkene selectivity toward the Zaitzev products is observed when the reaction is carried out in dichloroethane at reflux.

Cobalt co-catalysis for cross-electrophile coupling: Diarylmethanes from benzyl mesylates and aryl halides

The nickel-catalyzed cross-coupling of aryl halides with alkyl radicals derived from alkyl halides has recently been extended to couplings with carbon radicals generated by a co-catalyst. In this study, a new co-catalyst, cobalt phthalocyanine (Co(Pc)), is introduced and demonstrated to be effective for coupling substrates not prone to homolysis. This is because Co(Pc) reacts with electrophiles by an SN2 mechanism instead of by the electron-transfer or halogen abstraction mechanisms previously explored. Studies demonstrating the orthogonal reactivity of (bpy)Ni and Co(Pc), applying this selectivity to the coupling of benzyl mesylates with aryl halides, and the adaptation of these conditions to the less reactive benzyl phosphate ester and an enantioconvergent reaction are presented.

Nickel-Catalyzed Cross-Coupling of Anisoles with Alkyl Grignard Reagents via C-O Bond Cleavage

Nickel-catalyzed cross-coupling of methoxyarenes with alkyl Grignard reagents, which involves the cleavage of the C(aryl)-OMe bond, has been developed. The use of 1,3-dicyclohexylimidazol-2-ylidene as a ligand allows the introduction of a variety of alkyl groups, including Me, Me3SiCH2, ArCH2, adamantyl, and cyclopropyl. The method can also be used for the alkylative elaboration of complex molecules bearing a C(aryl)-OMe bond.

Copper-catalyzed alkene arylation with diaryliodonium salts

Alkenes and arenes represent two classes of feedstock compounds whose union has fundamental importance to synthetic organic chemistry. We report a new approach to alkene arylation using diaryliodonium salts and Cu catalysis. Using a range of simple alkenes, we have shown that the product outcomes differ significantly from those commonly obtained by the Heck reaction. We have used these insights to develop a number of new tandem and cascade reactions that transform readily available alkenes into complex arylated products that may have broad applications in chemical synthesis.

Modern Friedel-Crafts chemistry. Part-271. Alkylation of benzene with 1-benzyl- and 1-phenylcyclohexanols in the presence of H 2SO4 and AlCl3/CH3NO2 catalysts

The alkylation of benzyene with 1-benzylcyclohexanol (3) gave a mixture of 2,3-benzobicyclo[3.3.1]nona-2-ene (8, 79%) and cyclohexyldiphenylmethane (10, 21%) with AlCl3/CH3NO2 catalyst and a mixture of 1-benzylcyclohexene 5 (47.5%), 8 (8%), 10 (21.5%), 1-cyclopentyl-1,2- diphenylethane (12, 18%) and 1-benzyl-1-phenylcyclohexene (13, 4%) with H 2SO4 catalyst. Treatment of 3 with AlCl 3/CH3NO2 in petroleum ether gave a mixture of 5 (26%) and 8 (62%). Attempted alkylation of benzene with 1-phenylcyclohexanol (4) in the presence of either AlCl3/CH3NO2 or H2SO4 catalyst gave 1-(1-phenylcyclohexyl)-2- phenylcyclohexene (17) as sole product. Mechanistic interpretation of the results in terms of carbocation behaviour is offered.

Disproportionation of diarylmethanol derivatives by using supercritical water

Non-catalytic disproportionation of diarylmethanol derivatives was found to proceed efficiently in supercritical water. This method was also applied to various diarylmethylamine derivatives to give the disproportionation products in good yields.

Enantioselective protonation of samarium enolates derived from α- heterosubstituted ketones and lactone by SmI2-mediated reduction

SmI2-mediated reductive cleavage of α-heterosubstituents of α-alkyl or α-aryl ketones and lactone gave the corresponding 'thermodynamic samarium enolates'. Enantioselective protonation of the samarium enolates with C2- symmetric chiral diols afforded the corresponding ketones and lactone in moderate to high enantioselectivities.

Integrated chemical process. Construction of highly substituted allylic moieties from allylic sulfones in one-pot

According to 'integrated chemical process', a novel one-pot process for construction of highly substituted allylic moieties has been achieved. A series of alkylation of allylic sulfones and palladium-catalyzed reductive desulfonylation by use of LiBHEt3 is integrated. The double alkylation furnishes more substituted olefins. Use of arylzinc compounds in place of the hydride enables electrophilic alkylation/nucleophilic arylation in one-pot. The integrated process provides higher overall yields than the corresponding stepwise process.

New efficient nickel- and palladium-catalyzed cross-coupling reactions mediated by tetrabutylammonium iodide

(formula presented) The addition of Bu4NI has been found to accelerate the palladium(0)-catalyzed cross-coupling between benzylic zinc bromides and aryl or alkenyl triflates. Remarkably, it further allows a new nickel(0)-catalyzed cross-coupling between functionalized benzylic zinc reagents and primary alkyl iodides leading to polyfunctional products in good yields under mild reaction conditions (0-20 °C, 4-16 h).

Free radical chemistry of β-lactones. Arrhenius parameters for the decarboxylative cleavage and ring expansion of 2-oxetanon-4-ylcarbinyl radicals. Facilitation of chain propagation by catalytic benzeneselenol

2-Oxetanon-4-ylcarbinyl radicals undergo facile ring opening with cleavage of the C-O bond to give 3-butenoxyl radicals which in turn suffer loss of carbon dioxide to provide allyl radicals. When the initial radical is generated from a bromolactone with Bu3SnH and AIBN, chain propagation is poor owing to the relatively slow abstraction of hydrogen from the stannane by the allyl radical. The inclusion of catalytic Ph2Se2, reduced in situ to PhSeH, provides for much smoother cleaner reactions because of the better hydrogen donating capacity of the selenol. The oxetanon-4-ylcarbinyl radical derived from 6-benzyl-1-(bromomethyl)-8-oxa-7-oxobicyclo[4.2.0]octane is anomalous and undergoes a radical ring expansion in competition with the fragmentation process. Possible reasons for this anomaly are presented as are Arrhenius functions for the fragmentation and rearrangement. The Arrhenius function for the fragmentation of a simple 2-oxetanon-4-yl radical is also presented. Conditions are described under which the fragmentation of 2- oxetanon-4-yl radicals may be suppressed.