4277-27-4

Upstream product

• 6876-23-9 1,2-trans-dimethylcyclohexane 
• 1674-10-8 1,2-dimethylcyclohexene 
• 1759-64-4 1,6-dimethyl-1-cyclohexene 
• 132973-81-0 Lithium; octa-1,7-dien-3-olate 
• 2207-01-4 cis-1,2-dimethylcyclohexane 
• 1551-89-9 trans-2,3-dimethylcyclohexanone 
• 2808-75-5 2-methyl-1-methylenecyclohexane 
• 526-75-0 2,3-Dimethylphenol 
• 203319-65-7 (1R,2R)-1,2-Dimethyl-cyclohexane 
• 1551-88-8 cis-2,3-dimethylcyclohexanone 
• 4277-08-1 (+/-)-2c,3c-dimethyl-cyclohexan-r-ol 

Downstream Products

• 1551-89-9 trans-2,3-dimethylcyclohexanone 

Relevant academic research and scientific papers

Stereoselective oxidation of alkanes with: M -CPBA as an oxidant and cobalt complex with isoindole-based ligands as catalysts

Two complexes with isoindole-core ligands of general formula [M{C6H4C(NH2)NC(ONCMe2)2}2](NO3)2 (M = Co for 1 and M = Ni for 2) were studied as catalysts for the mild stereoselective alkane oxidation with m-chloroperbenzoic acid (m-CPBA) as an oxidant and cis-1,2-dimethylcyclohexane (cis-1,2-DMCH) as a main model substrate. Complex 1 disclosed a pronounced activity, with high retention of stereoconfiguration of substrates (>98% for cis-1,2-DMCH) and highest cis/trans ratio of tertiary alcohols (products) of 56, under mild conditions. The best achieved yields of tertiary cis-alcohols were of 13.7 and 50.5%, based on the substrate (cis-1,2-DMCH) and the oxidant (m-CPBA) respectively. Kinetic experiments, high bond and stereoselectivity parameters, kinetic isotope effect of 7.2(2) in the oxidation of cyclohexane, and incorporation of 18O from H218O support the involvement of CoIVO high-valent metal-oxo intermediates as main C-H attacking species.

Catalytic oxidation of alkanes by a (salen)osmium(VI) nitrido complex using H2O2 as the terminal oxidant

The osmium(vi) nitrido complex, [OsVI(N)(L)(CH3OH)]+ (1, L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion) is an efficient catalyst for the oxidation of alkanes under ambient conditions using H2O2 as the oxidant. Alkanes are oxidized to the corresponding alcohols and ketones, with yields up to 75% and turnover numbers up to 2230. Experimental and computational studies are consistent with a mechanism that involves O-atom transfer from H2O2 to [OsVI(N)(L)]+ to generate an [OsVIII(N)(O)(L)]+ active intermediate.

P450-catalyzed regio- and stereoselective oxidative hydroxylation of disubstituted cyclohexanes: Creation of three centers of chirality in a single CH-activation event This paper is dedicated to the memory of Harry H. Wasserman

Wild-type P450-BM3 is able to catalyze in a highly regio- and diastereoselective manner the oxidative hydroxylation of non-activated disubstituted cyclohexane derivatives lacking any functional groups, including cis- and trans-1,2-dimethylcyclohexane, cis- and trans-1,4-dimethylcyclohexane, and trans-1,4-methylisopropylcyclohexane. In all cases except chiral trans-1,2-dimethylcyclohexane as substrate, the single hydroxylation event at a methylene group induces desymmetrization with simultaneous creation of three centers of chirality. Certain mutants increase selectivity, setting the stage for future directed evolution work.

Catalyst-controlled aliphatic c-h oxidations with a predictive model for site-selectivity

Selective aliphatic C-H bond oxidations may have a profound impact on synthesis because these bonds exist across all classes of organic molecules. Central to this goal are catalysts with broad substrate scope (small-molecule-like) that predictably enhance or overturn the substrate's inherent reactivity preference for oxidation (enzyme-like). We report a simple small-molecule, non-heme iron catalyst that achieves predictable catalyst-controlled site-selectivity in preparative yields over a range of topologically diverse substrates. A catalyst reactivity model quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst.

Selective activation of secondary C-H bonds by an iron catalyst: Insights into possibilities created by the use of a carboxyl-containing bipyridine ligand

In this work, we report the discovery of a carboxyl-containing iron catalyst 1 (FeII-DCBPY, DCBPY = 2,2′-bipyridine-4,4′- dicarboxylic acid), which could activate the C-H bonds of cycloalkanes with high secondary (2°) C-H bond selectivity. A turnover number (TN) of 11.8 and a 30% yield (based on the H2O2 oxidant) were achieved during the catalytic oxidation of cyclohexane by 1 under irradiation with visible light. For the transformation of cycloalkanes and bicyclic decalins with both 2° and tertiary (3°) C-H bonds, 1 always preferred to oxidise the 2° C-H bonds to the corresponding ketone and alcohol products; the 2°/3° ratio ranged between 78/22 and >99/1 across 7 examples. 18O isotope labelling experiments, ESR experiments, a PPh3 method and the catalase method were used to characterize the reaction process during the oxidation. The success of 1 showed that, in addition to using a bulky catalyst, high 2° C-H bond selectivity could also be achieved using a less bulky molecular iron complex as the catalyst.

Oxidation of alkane using Pt/Eu2O3/TiO 2/SiO2 catalyst with O2 and H2 in acetic acid under mild conditions

A new solid catalyst of Pt/Eu2O3/TiO 2/SiO2 for oxidation of alkane was developed. Oxidation of adamantane using the multi-components supported catalyst with O2 and H2 was studied in acetic acid at 313 K. Several multi-components supported catalysts were prepared and tested the oxidation activity. It is found that loading order of Eu2O3, TiO2 and Pt on the SiO2 support strongly affected the oxidation catalysis. The active catalysts model was proposed from TEM-EDS analysis that very small Pt particles well dispersed on amorphous Eu2O3 and TiO 2 on the SiO2 support. Eu and Ti oxides concertedly activated O2 with electrons supplied from H2 on Pt, and active oxygen species efficiently oxidized adamantane and other alkanes to oxygenated compounds. Active oxygen species could not be identified but its reactivity was studied. It showed radical nature for oxidation of alkanes and a cleavage of C-H bond was the rate-determining step during the oxidation.

Oxidation with the "H2O2 - Manganese(IV) complex - Carboxylic acid" reagent 1. Oxidation of saturated hydrocarbons with peroxy acids and hydrogen peroxide

The complex [LMnIV(O)3MnIVL](PF6)2 (1), where L is 1,4,7-trimethyl-1,4,7-triazacyclononane, catalyzes a highly efficient stereoselective oxygenation of saturated hydrocarbons in the presence of H2O2. A carboxylic acid is an obligatory component of the reaction mixture, while acetonitrile or acetone can be used as solvent. The reaction occurs, forming alkyl hydroperoxide, ketone, and alcohol. Substitution at the tertiary carbon atom proceeds more easily than that at the secondary carbon atom, whereas primary C-H bonds are rather inactive. Oxidation of alkanes and alcohols with peroxy acids catalyzed by complex 1 occurs with lower efficiency.

Efficient stereoselective oxygenation of alkanes by peroxyacetic acid or hydrogen peroxide and acetic acid catalysed by a manganese(IV) 1,4,7- trimethyl-1,4,7-triazacyclononane complex

The dinuclear manganese complex [LMn(IV)(O)3Mn(IV)L](PF6)2, where L is 1,4,7-trimethyl-1,4,7-triazacyclononane. catalyses the oxygenation of alkane by peroxyacetic acid or by H2O2 in the presence of acetic acid to give alkanols, alkanones and alkyl hydroperoxides. The reactions can give large turnovers (up to 1350 after 1 h at 20°C) and can occur with a high degree of retention of stereochemistry at tertiary carbon atoms.