3325-80-2

Upstream product

• 19311-30-9 4-tert-butyl-1-methylcyclohexyl chloride 
• 13294-73-0 1-tert-butyl-4-methylenecyclohexane 
• 71340-37-9 Acetic acid (1S,2S,5R)-5-tert-butyl-2-methyl-cyclohexyl ester 
• 98-53-3 4-tercbutyl-cyclohexanone 
• 6353-54-4 4-tert-butyl-1-methylcyclohexanol 
• 86509-69-5 tert-Butylperoxy-oxo-acetic acid (1S,2S,5R)-5-tert-butyl-2-methyl-cyclohexyl ester 
• 37720-60-8 r-3-t-butyl-c-6-methylcyclohexene 
• 3419-74-7 4-tert-Butyl-1-methylcyclohex-1-en 
• 7453-05-6 toluene-4-sulfonic acid-(trans-4-tert-butyl-cyclohexyl ester) 
• 917-54-4 methyllithium 

Downstream Products

• 65199-18-0 4-tert-Butyl-1-fluoro-1-methyl-cyclohexane 
• 107743-14-6 1-tert-Butyl-1-fluoro-4-methyl-cyclohexane 
• 141077-77-2 4-tert-Butyl-1-dichloromethyl-1-methyl-cyclohexane 

Relevant academic research and scientific papers

Heterogenous Catalysis in Organic Chemistry. 2. A Mechanistic Comparison of Noble-Metal Catalysts in Olefin Hydrogenation

Product stereochemistry, double-bond isomerization, deuterium incorporation, and hydrogen uptake data were obtained for the hydrogenation/deuteration of a number of cyclic olefins over the various supported noble-metal catalysts.The data from the Pt-catal

STEREOCHEMISTRY ON THE CATALYTIC HYDROGENATION OF 1-t-BUTYL-4-METHYLENECYCLOHEXANE OVER MODIFIED RANEY Ni, Co, AND Fe CATALYSTS.

Contrary to a fresh catalyst, aged Raney Ni in ethanol provided exclusively a less stable product in the hydrogenation of 1-t-Butyl-4-methylene cyclohexane. A similar stereoselectivity was observed over a catalyst which was refluxed in ethanol as well as

Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen

The synthesis of weak chemical bonds at or near thermodynamic potential is a fundamental challenge in chemistry, with applications ranging from catalysis to biology to energy science. Proton-coupled electron transfer using molecular hydrogen is an attractive strategy for synthesizing weak element–hydrogen bonds, but the intrinsic thermodynamics presents a challenge for reactivity. Here we describe the direct photocatalytic synthesis of extremely weak element–hydrogen bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol?1. Key to this approach is the bifunctional behaviour of the chromophoric iridium hydride photocatalyst. Activation of molecular hydrogen occurs in the ground state and the resulting iridium hydride harvests visible light to enable spontaneous formation of weak chemical bonds near thermodynamic potential with no by-products. Photophysical and mechanistic studies corroborate radical-based reaction pathways and highlight the uniqueness of this photodriven approach in promoting new catalytic chemistry. [Figure not available: see fulltext.].

Highly Selective Hydrogenation of C═C Bonds Catalyzed by a Rhodium Hydride

Under mild conditions (room temperature, 80 psi of H2) Cp*Rh(2-(2-pyridyl)phenyl)H catalyzes the selective hydrogenation of the C═C bond in α,β-unsaturated carbonyl compounds, including natural product precursors with bulky substituents in the β position and substrates possessing an array of additional functional groups. It also catalyzes the hydrogenation of many isolated double bonds. Mechanistic studies reveal that no radical intermediates are involved, and the catalyst appears to be homogeneous, thereby affording important complementarity to existing protocols for similar hydrogenation processes.

Visible-Light-Enhanced Cobalt-Catalyzed Hydrogenation: Switchable Catalysis Enabled by Divergence between Thermal and Photochemical Pathways

The catalytic hydrogenation activity of the readily prepared, coordinatively saturated cobalt(I) precatalyst, (R,R)-(iPrDuPhos)Co(CO)2H ((R,R)-iPrDuPhos = (+)-1,2-bis[(2R,5R)-2,5-diisopropylphospholano]benzene), is described. While efficient turnover was observed with a range of alkenes upon heating to 100 °C, the catalytic performance of the cobalt catalyst was markedly enhanced upon irradiation with blue light at 35 °C. This improved reactivity enabled hydrogenation of terminal, di-, and trisubstituted alkenes, alkynes, and carbonyl compounds. A combination of deuterium labeling studies, hydrogenation of alkenes containing radical clocks, and experiments probing relative rates supports a hydrogen atom transfer pathway under thermal conditions that is enabled by a relatively weak cobalt-hydrogen bond of 54 kcal/mol. In contrast, data for the photocatalytic reactions support light-induced dissociation of a carbonyl ligand followed by a coordination-insertion sequence where the product is released by combination of a cobalt alkyl intermediate with the starting hydride, (R,R)-(iPrDuPhos)Co(CO)2H. These results demonstrate the versatility of catalysis with Earth-abundant metals as pathways involving open-versus closed-shell intermediates can be switched by the energy source.

Simple, chemoselective hydrogenation with thermodynamic stereocontrol

Few methods permit the hydrogenation of alkenes to a thermodynamically favored configuration when steric effects dictate the alternative trajectory of hydrogen delivery. Dissolving metal reduction achieves this control, but with extremely low functional group tolerance. Here we demonstrate a catalytic hydrogenation of alkenes that affords the thermodynamic alkane products with remarkably broad functional group compatibility and rapid reaction rates at standard temperature and pressure.

Diastercoselectivity in the heterogeneous hydrogenation reactions of phosphorous substituted olefins

Phosphorous substituted methylenecyclohexane olefins show enhanced diastereoselectivity in heterogeneous hydrogenation reactions using Pd/C. A model system derived from 4-t-butylcyclohexanone was used to explore the effects of solvent polarity and catalys

Organolanthanide catalyzed hydrogenation and hydrosilylation of substituted methylenecycloalkanes

This communication presents a study of the scope of the catalytic hydrogenation and hydrosilylation of chiral exomethylene-substituted cyclopentanes and cyclohexanes utilizing the organolanthanide precatalysts Cp2* LnCH(SiMe3)2 (Cp* = C5Me5; Ln = Sm, Yb). Both reaction types are sterically driven and lead to the cis-diastereomer as the major product. Additionally, the hydrosilylation is regiospecific, the silane being placed exclusively at the terminal position of the double bond.

REGIO- AND STEREO-SELECTIVITIES IN THE TITANIUM COMPLEX CATALYZED HYDROBORATION OF CARBON-CARBON DOUBLE BONDS IN VARIOUS UNSATURATED COMPOUNDS

The titanium complex prepared from TiCl3 and NaBH4 in THF in the presence of 18-crown-6 promotes the catalytic hydroboration of carbon-carbon double bonds in alkenes, alkadienes and unsaturated ethers with NaBH4, giving sodium organoborates which can be converted into alcohols by oxidation with H2O2/CH3ONa.The reaction proceeds with high regio- and stereo-selectivities.

Stereoelectronic Effects in Hydrogen-atom Transfer Reactions of Substituted Cyclohexyl Radicals

Thermolysis of the peroxyoxalates (1)-(7) and the diacyl peroxides (8)-(11) in cyclohexane at 100 deg C gives cycloalkenes and cycloalkanes by hydrogen-atom transfer reactions of the initially formed conformationally biased 4-t-butyl-, 4-t-butyl-cis,cis-2,6-dimethyl-, 4-t-butyl-cis,trans-2,6-dimethyl-, 4-t-butyl-cis-2-methyl-, 4-t-butyl-trans-2-methyl-, and 5-t-butyl-cis-2-methylcyclohexyl radicals (12)-(17).The composition of the product mixtures indicates that transfer of axial β-hydrogen atoms occurs more rapidly than does transfer of equatorial β-hydrogen atoms.These results support the hypothesis that homolytic fission of a C-H bond is favoured when it lies chlose to the plane of an adjacent semi-occupied orbital.