29790-29-2

Usage

Synthesis Reference(s)

Tetrahedron Letters, 32, p. 1741, 1991 DOI: 10.1016/S0040-4039(00)74318-8

InChI:InChI=1S/C13H18O2/c1-9-7-11(15)8-13(3,4)12(9)6-5-10(2)14/h5-6H,7-8H2,1-4H3/b6-5+

Upstream product

• 79-77-6 (E)-β-ionone 
• 534-22-5 2-methylfuran 
• 1193-79-9 2-acetyl-5-methylfuran 
• 59482-67-6 3-Benzenesulfonylmethyl-2,4,4-trimethyl-cyclohex-2-enol 
• 37677-82-0 (Z)-4-oxo-β-ionone 
• 79-77-6 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one 
• 56691-74-8 {[(2,6,6-trimethyl-1-cyclohexen-1-yl)methyl]sulfonyl}benzene 
• 66408-56-8 3-(1-Benzenesulfonyl-3-hydroxy-butyl)-2,4,4-trimethyl-cyclohex-2-enol 
• 125254-37-7 dimethyl 2-<1-methyl-1-(5-methylfuran-2-yl)ethyl>propane-1,3-dioate 
• 125254-53-7 2-diazo-6-methyl-6-(5-methylfuran-2-yl)heptan-3-one 
• 125254-45-7 1-diazo-4-methyl-4-(5-methylfuran-2-yl)pentan-2-one 
• 125254-48-0 methyl 4-methyl-4-(5-methylfuran-2-yl)pentanoate 
• 125254-50-4 4-methyl-4-(5-methylfuran-2-yl)pentanoyl chloride 
• 125254-49-1 4-methyl-4-(5-methylfuran-2-yl)pentanoic acid 

Downstream Products

• 69659-83-2 4-Oxo-β-jonon-9-(aethylenacetal) 
• 80713-56-0 4-Oxo-β-jonon-4,9-bis(aethylenacetal) 
• 29790-30-5 (7E,9ε)-9-hydroxy-5,7-megastigmadien-4-one 
• 224046-67-7 (2E,4E)-2-Fluoro-3-methyl-5-(2,6,6-trimethyl-3-oxo-cyclohex-1-enyl)-penta-2,4-dienal 
• 200860-83-9 all-trans-4-keto-10F-β-ionylideneacetaldehyde 
• 200860-81-7 Acetic acid 4-((1E,3Z,5E,7E,9E,11E)-4-fluoro-3,7,12-trimethyl-13-oxo-trideca-1,3,5,7,9,11-hexaenyl)-3,5,5-trimethyl-2-oxo-cyclohex-3-enyl ester 
• 74285-60-2 (+/-)-3-Acetoxy-4-oxo-β-jonon-9-(aethylenacetal) 
• 74285-61-3 (+/-)-3-Hydroxy-4-oxo-β-jonon 
• 74311-44-7 (S)-3-Hydroxy-4-oxo-β-jonon 
• 80779-52-8 (R)-3-Hydroxy-4-oxo-β-jonon 
• 882491-37-4 (6S)-6-hydroxy-3-[(1E)-3-hydroxy-3-methylpenta-1,4-dienyl]-2,4,4-trimethylcyclohex-2-en-1-one 
• 74285-59-9 (E)-3,5,5-trimethyl-2-oxo-4-(3-oxobut-1-en-1-yl)cyclohex-3-en-1-yl acetate 
• 74311-42-5 (S)-3-Acetoxy-4-oxo-β-jonon 

Relevant academic research and scientific papers

Solvent-free aerobic chemoselective oxidation of β-ionone catalyzed by N-hydroxyphthalimide/Co(acac)2

β-Ionone was oxidized with O2 under solvent-free conditions catalyzed by an N-hydroxyphthalimide/Co(acac)2 system in mild conditions with high conversion and excellent selectivity to oxo-β-ionone or 5,6-epoxy-β-ionone in different reaction conditions, respectively. Copyright Taylor & Francis Group, LLC.

Method for preparing cyclic alpha, beta-unsaturated ketone

The invention provides a method for preparing cyclic alpha, beta-unsaturated ketone. According to the method, a compound shown in the formula (I) is oxidized by oxygen through electrochemical synthesis in the presence of a catalyst and an auxiliary agent to prepare a compound shown in the formula (II). The method is mild in condition, high in atom economy and less in three wastes, and the productyield is higher than 95%.

Selective oxygenation of ionones and damascones by fungal peroxygenases

Apocarotenoids are among the most highly valued fragrance constituents, being also appreciated as synthetic building blocks. This work shows the ability of unspecific peroxygenases (UPOs, EC1.11.2.1) from several fungi, some of them being described recently, to catalyze the oxyfunctionalization of α- and β-ionones and α- and β-damascones. Enzymatic reactions yielded oxygenated products such as hydroxy, oxo, carboxy, and epoxy derivatives that are interesting compounds for the flavor and fragrance and pharmaceutical industries. Although variable regioselectivity was observed depending on the substrate and enzyme, oxygenation was preferentially produced at the allylic position in the ring, being especially evident in the reaction with α-ionone, forming 3-hydroxy-α-ionone and/or 3-oxo-α-ionone. Noteworthy were the reactions with damascones, in the course of which some UPOs oxygenated the terminal position of the side chain, forming oxygenated derivatives (i.e., the corresponding alcohol, aldehyde, and carboxylic acid) at C-10, which were predominant in the Agrocybe aegerita UPO reactions, and first reported here.

Fungi-mediated biotransformation of the isomeric forms of the apocarotenoids ionone, damascone and theaspirane

In this work, we describe a study on the biotransformation of seven natural occurring apocarotenoids by means of eleven selected fungal species. The substrates, namely ionone (α-, β- and γ-isomers), 3,4-dehydroionone, damascone (α- and β-isomers) and theaspirane are relevant flavour and fragrances components. We found that most of the investigated biotransformation reactions afforded oxidized products such as hydroxy- keto- or epoxy-derivatives. On the contrary, the reduction of the keto groups or the reduction of the double bond functional groups were observed only for few substrates, where the reduced products are however formed in minor amount. When starting apocarotenoids are isomers of the same chemical compound (e.g., ionone isomers) their biotransformation can give products very different from each other, depending both on the starting substrate and on the fungal species used. Since the majority of the starting apocarotenoids are often available in natural form and the described products are natural compounds, identified in flavours or fragrances, our biotransformation procedures can be regarded as prospective processes for the preparation of high value olfactory active compounds.

Method for efficiently preparing oxo-ionone

The invention discloses a method for efficiently preparing oxo-ionone. The method uses manganese dioxide as a catalyst, and oxo-ionone is obtained by catalytic oxidation at an allylic position of ionone. Oxo-ionone can be synthesized in high yield by the method, the operation is simple, the cost is low, and the method is green and environment-friendly.

MnO2/TBHP: A Versatile and User-Friendly Combination of Reagents for the Oxidation of Allylic and Benzylic Methylene Functional Groups

In the presence of activated MnO2, tert-butyl hydroperoxide (TBHP) in CH2Cl2 is able to oxidize the allylic and benzylic methylene groups of different classes of compounds. I describe a one-pot oxidation protocol based on two sequential steps. In the first step, carried out at low temperature, MnO2 catalyses the oxidation of the methylene group. This is followed by a second step where reaction temperature is increased, allowing MnO2 both to catalyse the decomposition of unreacted TBHP and to oxidize allylic alcohols that could possibly be formed. The proposed oxidation procedure is generally applicable, although its efficiency, regioselectivity, and chemoselectivity are strongly dependent on the structure of the substrate. A simple and user-friendly synthetic procedure for the oxidation of allylic and benzylic methylene groups to the corresponding conjugated carbonyl derivatives is described. The proposed oxidation protocol is based on the combined use of MnO2 and tert-butyl hydroperoxide, and is generally applicable.

Rh2(esp)2-catalyzed allylic and benzylic oxidations

The dirhodium(ii) catalyst Rh2(esp)2 allows direct solvent-free allylic and benzylic oxidations by T-HYDRO with a remarkably low catalyst loading. This method is operationally simple and scalable at ambient temperature without the use of any additives. The high catalyst stability in these reactions may be attributed to a dirhodium(ii,ii) catalyst resting state, which is less prone to decomposition.

Co(acac)catalyzed allylic and benzylic oxidation by tert -butyl hydroperoxide

Various allylic and benzylic substrates were oxidized to the corresponding enones, arenealdehydes and aryl ketones in good yields with tert-butyl hydroperoxide in the presence of catalytic amounts of Co(acac)under mild conditions. The reactivity, selectivity, and scope of the reaction were investigated. Georg Thieme Verlag Stuttgart. New York.

Non-heme iron catalysis in CC, C-H, and CH2 oxidation reactions. Oxidative transformations on terpenoids catalyzed by Fe(bpmen)(OTf)2

The oxidation of terpene olefins with hydrogen peroxide in the presence of the non-hemo catalyst 5a afforded mixtures of epoxides whose composition was dependent upon the oxidation protocol used in each case. With terpenoid enones, the mixtures obtained evolved from clean epoxidation of α-ionone 23 to the clean allylic oxidation of damascone 28 due to the progressive deactivation of the electron density on the double bonds present in this series. The oxidation of bicyclic and tricyclic terpenoids afforded oxidation products coming from epoxidation, to olefin degradation, methyne and methylene activation products. Probably, the most attractive result was the synthesis of the Magnus lactone 46, from the tricyclic ether 45, with 88% yield and 100% conversion.

Studies on the enantioselective oxidation of β-ionone with a whole E. coli system expressing cytochrome P450 monooxygenase BM3

Recombinant Escherichia coli cells, expressing an NADH-dependent cytochrome P450 monooxygenase BM-3 mutant, were used for the hydroxyalation of the sesquiterpenoid β-ionone to (R)-4-hydroxy-β-ionone. The decrease in enantioselectivity of cytochrome P450 monooxygenase BM-3 catalyzed hydroxylation of β-ionone can be ascribed to the overoxidation of the desired product. In this initial study we report, that by addressing reaction conditions the enantiomeric excess can be increased and the overoxidation can be reduced. Furthermore, we report herein the kinetic resolution of racemic 4-hydroxy-β-ionone using the same P450 monooxygenase for the production of (S)-4-hydroxy-β-ionone. Although the enantioselectivity of the enzyme is rather low for this reaction, this reaction could be of interest with improved P450 BM-3 variants. Both systems need further investigations and optimizations for preparative application.