6328-22-9

Usage

Uses

Used in Pharmaceutical Industry:
3-Propan-2-ylcyclohex-2-en-1-one is used as a reagent in the enantioselective total synthesis of complex organic molecules, such as natural products and pharmaceutical compounds. Its application in this field is due to its ability to participate in selective reactions that can lead to the formation of desired enantiomers, which are crucial for the development of effective drugs with minimal side effects.
Used in Enzymatic Synthesis:
In the field of biochemistry and enzymatic synthesis, 3-propan-2-ylcyclohex-2-en-1-one is utilized in the enantioselective total synthesis of nigelladine A, a complex molecule with potential biological activities. The use of an engineered P450 enzyme in this process allows for late-stage C-H oxidation, which is a crucial step in the synthesis of nigelladine A. This application highlights the compound's role in facilitating the development of novel and complex bioactive molecules.

InChI:InChI=1/C9H14O/c1-7(2)8-4-3-5-9(10)6-8/h6-7H,3-5H2,1-2H3

Upstream product

• 3983-08-2 3-isopropylcyclohexene 
• 4292-04-0 1-isopropylcyclohexene 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 920-39-8 isopropylmagnesium bromide 
• 20023-39-6 (5-isopropyl-cyclohexa-1,4-dienyl)-methyl ether 
• 108-24-7 acetic anhydride 
• 43025-83-8 diethyl-methyl-(3-oxo-butyl)-ammonium; iodide 
• 7152-15-0 ethyl 4-methyl-3-oxo-pentanoate 
• 26823-12-1 2,2-Dimethyl-3,7-dioxo-octanoic acid ethyl ester 
• 925-90-6 ethylmagnesium bromide 
• 32830-98-1 1-chloro-4-methyl-pentan-3-one 
• 141-97-9 ethyl acetoacetate 
• 109-74-0 propyl cyanide 
• 16566-96-4 5,7,7-trimethyl-6,8-dioxabicyclo<3.2.1>octane 

Downstream Products

• 108247-03-6 <3-Isopropyl-cyclohexa-2,5-dien-yl>-essigsaeure-aethylester 
• 23396-36-3 3-isopropylcyclohexanone 
• 74006-76-1 (R)-(+)-3-(1-methylethyl)cyclohexanone 
• 23396-36-3 (3S)-3-isopropylcyclohexanone 
• 1097631-13-4 1-butyl-3-isopropylcyclohex-2-en-1-ol 
• 1312208-25-5 (R)-3-isopropyl-3-(nitromethyl)cyclohexanone 
• 1289576-77-7 (R)-3-phenyl-3-iso-propylcyclohexanone 
• 1227936-31-3 (rac)-3-phenyl-3-isopropylcyclohexanone 

Relevant academic research and scientific papers

Development of a Kilogram-Scale Process for the Enantioselective Synthesis of 3-Isopropenyl-cyclohexan-1-one via Rh/DTBM-SEGPHOS-Catalyzed Asymmetric Hayashi Addition Enabled by 1,3-Diol Additives

The development of a scalable process for the Rh-catalyzed asymmetric 1,4-addition of (isopropenyl)pinacolboronate to 2-cyclohexen-1-one is reported. High-throughput ligand screening and initial optimization studies identified DTBM-SEGPHOS as an effective ligand along with a heptane/MeOH mixed solvent system. An inhibitory effect of the pinacol byproduct was identified, which could be mitigated by the addition of a 1,3-diol such as neopentyl glycol (npg). This process was demonstrated on 1 kg scale with 0.6 mol % Rh, producing (S)-1 in 82% yield and 99.6% ee, and was successfully scaled up at a vendor on 100 kg scale.

Enantioselective Total Synthesis of Nigelladine A via Late-Stage C-H Oxidation Enabled by an Engineered P450 Enzyme

An enantioselective total synthesis of the norditerpenoid alkaloid nigelladine A is described. Strategically, the synthesis relies on a late-stage C-H oxidation of an advanced intermediate. While traditional chemical methods failed to deliver the desired outcome, an engineered cytochrome P450 enzyme was employed to effect a chemo- and regioselective allylic C-H oxidation in the presence of four oxidizable positions. The enzyme variant was readily identified from a focused library of three enzymes, allowing for completion of the synthesis without the need for extensive screening.

Palladium-catalyzed saegusa-ito oxidation: Synthesis of α,β-Unsaturated carbonyl compounds from trimethylsilyl enol ethers

Palladium-catalyzed Saegusa-Ito oxidation of trimethylsilyl enol ethers is possible using Oxone as a stoichiometric oxidant and sodium hydrogen phosphate as a buffer. Cyclic and acyclic enones as well as α,β-unsaturated aldehydes are obtained in good to excellent yields.

The cinchona primary amine-catalyzed asymmetric epoxidation and hydroperoxidation of α,β-unsaturated carbonyl compounds with hydrogen peroxide

Using cinchona alkaloid-derived primary amines as catalysts and aqueous hydrogen peroxide as the oxidant, we have developed highly enantioselective Weitz-Scheffer-type epoxidation and hydroperoxidation reactions of α,β-unsaturated carbonyl compounds (up to 99.5:0.5 er). In this article, we present our full studies on this family of reactions, employing acyclic enones, 5-15-membered cyclic enones, and α-branched enals as substrates. In addition to an expanded scope, synthetic applications of the products are presented. We also report detailed mechanistic investigations of the catalytic intermediates, structure-activity relationships of the cinchona amine catalyst, and rationalization of the absolute stereoselectivity by NMR spectroscopic studies and DFT calculations.

Pt-catalyzed oxidative rearrangement of cyclic tertiary allylic alcohols to enones using aqueous hydrogen peroxide

An oxidative rearrangement of cyclic tertiary allylic alcohols to β-disubstituted α,β-unsaturated ketones by Pt black catalyst with aqueous hydrogen peroxide is described. The reaction proceeds under organic solvent- and halide-free conditions and gives only water as a coproduct. The Pt black catalyst is commercially available and can be reused at least four times.

Stereoselective aziridination of cyclic allylic alcohols using chloramine-T

The stereoselective aziridination of a range of cyclic allylic alcohols using two different chloramine salts (4-MeC6H4SO 2NClNa, TsNClNa and t-BuSO2NClNa, BusNClNa) has been explored. The stereoselectivity of these reactions was highly dependent on the structure of the allylic alcohol and the chloramine salt. Generally, mixtures of cis- and trans-hydroxy aziridines were obtained, in which the major diastereomer was the cis-hydroxy aziridine, whilst complete cis- diastereoselectivity was observed in the aziridination of 1,3-disubstituted allylic alcohols. In each case studied, aziridination using BusNClNa gave higher cis-stereoselectivity than that observed for the same reaction using TsNClNa. Unexpectedly, application of the aziridination conditions to 1-substituted cyclopen-2-en-1-ols did not generate the aziridines. Instead, epoxy sulfonamides were obtained.

Highly efficient methods for the one-pot synthesis of β-substituted enones

A new mild and practically convenient one-pot procedure for the direct β-substitution of enones, developed using a conjugate addition-oxidation strategy with a full range of copper based reagents and N-tert- butylphenylsulfinimidoyl chloride, was analyzed. To start the investigation reaction of a simple Gilman cuprate, lithium di-n-butylcuprate, with cyclohex-2-enone was performed. The desired one-pot transformation was found to be achievable, albeit in a low 39% yield. The application of a series of individual organocuprate reagents was also investigated. It was observed that the technique provided good to excellent yields of β-substituted enones from all of the unsaturated starting materials employed.

Highly enantioselective transfer hydrogenation of α,β- unsaturated ketones

We describe an efficient and highly enantioselective conjugate transfer hydrogenation of α,β-unsaturated ketones that is catalyzed by a salt made from tert-butyl valinate and a recently introduced powerful chiral phosphoric acid catalyst (TRIP). Copyright

Assessing the Substrate Selectivities and Enantioselectivities of Eight Novel Baeyer-Villiger Monooxygenases toward Alkyl-Substituted Cyclohexanones

Genes encoding eight Baeyer-Villiger monooxygenases have recently been cloned from bacteria inhabiting a wastewater treatment plant. We have carried out a systematic investigation in which each newly cloned enzyme, as well as the cyclohexanone monooxygenase from Acinetobacter sp. NCIB 9871, was used to oxidize 15 different alkyl-substituted cyclohexanones. The panel of substrates included equal numbers of 2-, 3-, and 4-alkyl-substituted compounds to probe each enzyme's stereoselectivity toward a homologous series of synthetically important compounds. For all 4-alkyl-substituted cyclohexanones tested, enzymes were discovered that afforded each of the corresponding (S)-lactones in ≥98% ee. This was also true for the 2-alkyl-substituted cyclohexanones examined. The situation was more complex for 3-akyl-substituted cyclohexanones. In a few cases, single Baeyer-Villiger monooxygenases possessed both high regio- and enantioselectivities toward these compounds. More commonly, however, they showed only one type of selectivity. Nonetheless, enzymes with such properties might be useful as parts of a two-step bioprocess where an initial kinetic resolution is followed by a regioselective oxidation on the isolated, optically pure ketone.

Oxidation of silyl enol ethers by using IBX and IBX·N-oxide complexes: A mild and selective reaction for the synthesis of enones

α,β-Unsaturated carbonyl compounds can be prepared by the oxidation of trimethylsilyl enol ethers with IBX (1) or IBX·MPO (2). A diverse set of carbonyl compounds can be dehydrogenated with ease by using this method. Trimethylsilyl enol ethers such as 4, which are formed in situ by the addition of an organometallic species to an enone, can be dehydrogenated with 1 or 2 to give a functionalized enone (e. g. 3 → 5). IBX = iodoxybenzoic acid; MPO = 4-methoxypyridine-N-oxide.