790220-75-6

Usage

Stereochemistry

1R,2R configuration

Structure

Cyclohexane ring with a methyl and a phenyl group attached

Application

Chiral building block in organic synthesis and research

Role

Chiral auxiliary in asymmetric synthesis

Role

Substrate for various catalytic reactions

Importance

Unique stereochemical properties for development of new pharmaceuticals and fine chemicals

Potential applications

Development of new materials and chemical processes

Upstream product

• 4829-02-1 2-hydroxy-2-phenylcyclohexanone 
• 75-16-1 methylmagnesium bromide 
• 15288-87-6 1-phenylheptane-1,6-dione 
• 24400-75-7 ethylene-cetal de la bromo-5 pentanone-2 
• 94-02-0 ethyl 3-oxo-3-phenylpropionate 
• 268750-57-8 4-methyl-5-phenylocta-1,7-diene-4,5-diol 
• 579-07-7 1-Phenylpropane-1,2-dione 
• 51128-50-8 2-[(trimethylsilyl)oxy]cyclohex-2-en-1-one 
• 765-87-7 cyclohexane-1,2-dione 
• 1444-65-1 (RS)-2-phenylcyclohexanone 
• 678975-43-4 2-phenyl-2-((phenylamino)oxy)cyclohexan-1-one 
• 1041469-72-0 C₁₇H₂₈OSi₂ 
• 676-58-4 methylmagnesium chloride 

Relevant academic research and scientific papers

Direct Asymmetric α-Hydroxylation of Cyclic α-Branched Ketones through Enol Catalysis

Enantiopure α-hydroxy carbonyl compounds are common scaffolds in natural products and pharmaceuticals. Although indirect approaches towards their synthesis are known, direct asymmetric methodologies are scarce. Herein, we report the first direct asymmetric α-hydroxylation of α-branched ketones through enol catalysis, enabling a facile access to valuable α-keto tertiary alcohols. The transformation, characterized by the use of nitrosobenzene as the oxidant and a new chiral phosphoric acid as the catalyst, delivers a good scope and excellent enantioselectivities.

Bronsted Acid Mediated Direct α-Hydroxylation of Cyclic α-Branched Ketones

We report a Bronsted acid mediated direct α-hydroxylation of cyclic α-branched ketones via a tandem aminoxylation/N-O bond-cleavage process. Nitrosobenzene is used as the oxidant and subsequently promotes the liberation of the free alcohol. The desired pr

Unexpected TiIII/Mn-promoted pinacol coupling of ketones

Titanocene(III) chemistry has emerged in the last decades as an indispensable tool in C-C bond-forming reactions. In this context, pinacol and related reactions allow the stereoselective synthesis of vicinal diols. In this work, we present new applications of these reactions using as starting materials aromatic ketones. Simple and smooth reaction conditions have been developed and have been applied for inter- and intramolecular processes. We also describe that although Cp2TiCl is usually used as a monoelectronic reducing agent, it can be also used as an efficient Lewis acid.

Electroreductive crossed pinacol coupling of aromatic ketones with aliphatic ketones and aldehydes

The intermolecular crossed pinacol coupling of aromatic ketones with aliphatic aldehydes and ketones was effected by electroreduction in the presence of chlorotrimethylsilane. The best result was obtained using a Pb cathode in Bu4NPF6/sub

trans-Stereoselective intramolecular crossed pinacol coupling of aromatic 1,4-, 1,5-, and 1,6-diketones by electroreduction

Electroreduction of aromatic 1,4-, 1,5-, and 1,6-diketones in the presence of chlorotrimethylsilane and triethylamine gave four-, five-, and six-membered 1,2-diols with trans-stereoselectivity.

Intercalation of multiple carbon atoms between the carbonyls of α-diketones

The reaction of open-chain or cyclic α-diketones with specific ω-alkenyl organometallics leads readily under the proper conditions to 1,2-diols bonded to terminal olefinic chains. With 1-phenyl-1,2-propanedione, biacetyl, and cyclohexane-1,2-dione, allylindation in aqueous THF proceeds readily at both adjacent carbonyls. For cyclododecane-1,2-dione, recourse must be made to allylmagnesium bromide for completing the second-stage condensation. Grignard reagents have also served well as reactants for biacetyl monoadducts. In contrast, monoallylated camphorquinone is reluctant to couple to Grignard reagents and reacts only when Barbier-type alkyllithium reactions are applied. The ring closing metatheses of these products have been examined. Where six-membered ring formation operates, cyclization can be performed directly on diols. When larger rings are involved, the diols will react only if structural preorganization capable of facilitating mutual approach of the two double bonds is at play. For this purpose, the prior conversion to a cyclic carbonate holds considerable utility. In the latter setting, saponification must precede the diol cleavage step which has been performed with lead tetraacetate. The latter reagent also exhibits the very beneficial effect of facilitating removal of ruthenium and phosphorus byproducts generated during the metathesis step. This chemistry conveniently lends itself to the controlled intercalation of multiple methylene groups between the carbonyl carbons of readily available α-diketones to deliver linear or cyclic products.

Tandem deployment of indium-, ruthenium-, and lead-promoted reactions. Four-carbon intercalation between the carbonyl groups of open-chain and cyclic α-diketones

(equation presented) An efficient strategy for the conversion of 1,2-diketones into saturated 1,6-diketones and Δ2,3/Δ3,4-unsaturated congeners thereof is reported.

Oxidative Cleavage of vic-Diols Using Copper(II) Bromide-Lithium t-Butoxide: A New Route to Unsymmetrical 1,5- and 1,6-Diketones

Unsymmetrical 1,6-diketones were obtained by the copper(II) bromide-lithium t-butoxide oxidation of 1,2-disubstituted 1,2-cyclohexanediols. The diols were easily prepared by the addition of Grignard reagents to 2-trimethylsiloxy-2-cyelohexenone followed by the hydrolysis and treatment of the resulting 2-hydroxycyclohexanones with the second Grignard reagents. Similarly, 1,5-Diketones were obtained using 2-trimethylsiloxy-2-cyclopentenone as a starting material.