77613-91-3

Upstream product

• 16807-60-6 3-methoxycyclohex-2-en-1-one 
• 77613-90-2 Benzoic acid (1S,3R)-3-hydroxy-2,2-dimethyl-cyclohexyl ester 
• 562-13-0 2,2-dimethyl-1,3-cyclohexanedione 
• 1193-55-1 2-methylcyclohexane-1,3-dione 
• 77613-89-9 2,2-dimethyl-3-benzoyloxycyclohexanone 
• 1091626-88-8 cis-3-acetoxy-2,2-dimethylcyclohexyl acetate 

Downstream Products

• 121307-69-5 cis-1,3-bis(methansulfonyloxy)-2,2-dimethylcyclohexan 
• 1091626-89-9 (1R,3S)-3-hydroxy-2,2-dimethylcyclohexyl acetate 
• 1091626-88-8 cis-3-acetoxy-2,2-dimethylcyclohexyl acetate 
• 35934-83-9 3,3-dimethyl-1,4-cyclohexadiene 
• 114693-84-4 cis-2,2-dimethyl-1,3-cyclohexanediol bis(p-toluenesulfonate) 

Relevant academic research and scientific papers

Acylative desymmetrization of cyclic meso-1,3-diols by chiral DMAP derivatives

An efficient enantioselective acylative desymmetrization of cyclic meso-1,3-diols was developed by using a chiral DMAP derivative 1e having a 1,1¤-binaphthyl unit. The reactions required only 0.5mol% of the catalyst and showed good to excellent enantioselectivity. With this transformation, 5a, a key building block for the synthesis of natural products, was easily obtained in almost enantiomerically pure form after a single recrystallization. Control experiments revealed that tert-alcohol units on the catalyst were responsible for both the catalytic activity and enantioselectivity.

An unexpected directing effect in the asymmetric transfer hydrogenation of α,α-disubstituted ketones

α,α-Disubstituted ketones containing an aromatic ring or alkene are reduced in high enantiomeric excess using an asymmetric transfer hydrogenation catalyst. The sense of reduction indicates that the unsaturated region of the ketone adopts a position adjacent to the Ru-bound η6-arene ring in the reduction transition state.

Chemoenzymatic synthesis of both enantiomers of 3-hydroxy-2,2- dimethylcyclohexanone

(Chemical Equation Presented) The stereoselective acetylation of meso-2,2-dimethyl-1,3-cyclohexanediol by vinyl acetate in the presence of three lipases gave the (1R,3S)-monoester in high enantiomeric excess (ee ≥ 98%). The hydrolysis of the corresponding meso-diacetate in the presence of Candida antarctica lipase in phosphate buffer provided the opposite enantiomer. Optically active monoacetates were converted to both enantiomers of 3-hydroxy-2,2-dimethylcyclohexanone, a versatile chiral building block.

Efficient ruthenium-catalyzed transfer hydrogenation/hydrogenation of 1,3-cycloalkanediones to 1,3-cycloalkanediols using microwave heating

A number of 1,3-cycloalkanediones were efficiently reduced to the corresponding diols in good yield by the use of a ruthenium catalyst, 2-propanol, and hydrogen gas under microwave heating.

Aromatization of 1,4-Cyclohexadienes with Tetracyanoethylene: A Case of Varying Mechanisms

The aromatization of 1,4-cyclohexadiene and four alkyl-substituted 1,4-cyclohexadienes with tetracyanoethylene was examined and found in four of five cases to involve two competing mechanisms.Most of each reaction proceeded by concerted ene addition followed by breakdown of the ene product, probably heterolytically.Rate constans for diene reaction were determined in acetonitrile-d3 and p-dioxane-d8.Adducts were isolated in three cases and rate constants for adduct breakdown determined for isolated compounds.Where the adduct could be observed but not isolated, a constant was calculated through computer simulation of the rate data.The minor mechanism competing with the ene addition displayed not detectable intermediates and seemed most consistent with electron-proton-electron-proton or electron-proton-hydrogen-atom transfer.Total reaction rate varied by a factor of over 4 * 105, yet with one exception, the ratio of the two pathways varied very little.One possible explaonation for this, the presence of a common rate determining step preceding any hydrogen transfer (such as SET) was ruled out by the finding of a large primary isotope effect for hexadeuterio-1,4-cyclohexadiene disappearance (kH/kD = 5.2).With one diene, 3,3-dimethyl-1,4-cyclohexadiene, the otherwise minor mechanism became the sole one, as the adduct formed was clearly not a concerted ene adduct.However, in this case aromatization also required a 1,2 methyl shift, and the fact that quantitative collapse to an adduct, without rearrangement, occured instead ruled out a simple cation intermediate from hydride transfer.A reversible electron transfer therefore seems the likeliest first step for the minor mechanism.

Intramolecular hydride shift in some noncyclic isopropyl ketols

The acyclic ketols 711 and 812 have been synthesized by a Reformatsky sequence.Each ketol undergoes intramolecular hydride transfer when refluxed in KOH-H2O-t-BuOH solution.When the procedure was applied to the synthesis of 34, hydride transfer ocur