108944-32-7

Upstream product

• 127-41-3 alpha-ionone 
• 24190-29-2 (R)-α-ionone 
• 24190-29-2 (+)-(R)-α-Ionon 

Downstream Products

• 874001-10-2 4-Hydroxy-1.1.3-trimethyl-2-(3-hydroxy-butyl)-cyclohexan 
• 809237-15-8 (Z,1'RS,2'RS,3'SR)-4-(2',3'-epoxy-2',6',6'-trimethylcyclohexyl)-3-buten-2-one 
• 14398-34-6 4-(3-hydroxy-2,6,6-trimethylcyclohex-1-enyl)but-3-en-2-one 
• 97371-50-1 7-hydroxy-4,6,10,10-tetramethyl-5-oxatricyclo<4.4.0.0^1.4>dec-2-ene 
• 112379-22-3 4-<3-(1-Methoxy-2-bromoethoxy)-2,6,6-trimethylcyclohex-1-yl>-2-butanone 
• 112379-22-3 4-<3-(1-Methoxy-2-bromoethoxy)-2,6,6-trimethylcyclohex-1-yl>-2-butanone 
• 112379-29-0 4-(3-Ethenoxy-2,6,6-trimethylcyclohexen-1-yl)-2-butanone 
• 112893-58-0 4-<3-(1-Ethoxy-2-bromoethoxy)-2,6,6-trimethylcyclohexen-1-yl>-but-3-en-2-one 
• 112893-56-8 4-<3-(1-Ethoxy-2-bromoethoxy)-2,6,6-trimethyl-cyclohexen-1-yl>-2-butanone 
• 114298-66-7 2,4,4-trimethyl-3-vinyl-cyclohex-2-enol 
• 24190-29-2 (R)-α-ionone 
• 71629-15-7 4-(3-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one 
• 112379-21-2 4-(3-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone 
• 60078-92-4 2,4,4-trimethyl-3-formyl-2-cyclohexen-1-ol 

Relevant academic research and scientific papers

Total Synthesis of (+)-Granatumine A and Related Bislactone Limonoid Alkaloids via a Pyran to Pyridine Interconversion

We report the first total synthesis of (+)-granatumine A, a limonoid alkaloid with PTP1B inhibitory activity, in ten steps. Over the course of this study, two key methodological advances were made: a cost-effective procedure for ketone α,β-dehydrogenation using allyl-Pd catalysis, and a Pd-catalyzed protocol to convert epoxyketones to 1,3-diketones. The central tetrasubstituted pyridine is formed by a convergent Knoevenagel condensation and carbonyl-selective electrocyclization cascade, which was followed by a direct transformation of a 2H-pyran to a pyridine. These studies have led to the structural revision of two members of this family.

Oxidation of alkenes with non-heme iron complexes: Suitability as an organic synthetic method

In the course of a preliminary study to determine the preparative value and the synthetic applications of the non-heme iron(II) complexes Fe(bpmen)(OTf)2 and Fe(tpa)(OTf)2, in particular the oxidation of alkenes by using hydrogen peroxide as the terminal oxidant, we have found significant differences in catalyst behavior. After several attempts it was clear that the preparative relevance of the oxidation processes was linked to the concentration of the catalyst and optimal results were obtained when the concentration value was 5 mol %. At that concentration, the Fe(bpmen)(OTf)2 catalyst mostly gave rise to mixtures of the epoxide and the trans-dihydroxylation products formed by water-assisted hydrolytic cleavage of the epoxides. Furthermore, the use of the tripodal ligand tpa led to cis dihydroxylation products. When deactivated olefins were used as substrates for the oxidation reaction, the cis-diols were obtained exclusively, although with modest conversions, regardless of the catalyst used.

Sustainable catalytic protocols for the solvent free epoxidation and: Anti -dihydroxylation of the alkene bonds of biorenewable terpene feedstocks using H2O2 as oxidant

A tungsten-based polyoxometalate catalyst employing aqueous H2O2 as a benign oxidant has been used for the solvent free catalytic epoxidation of the trisubstituted alkene bonds of a wide range of biorenewable terpene substrates. This epoxidation protocol has been scaled up to produce limonene oxide, 3-carene oxide and α-pinene oxide on a multigram scale, with the catalyst being recycled three times to produce 3-carene oxide. Epoxidation of the less reactive disubstituted alkene bonds of terpene substrates could be achieved by carrying out catalytic epoxidation reactions at 50 °C. Methods have been developed that enable direct epoxidation of untreated crude sulfate turpentine to afford 3-carene oxide, α-pinene oxide and β-pinene oxide. Treatment of crude epoxide products (no work-up) with a heterogeneous acid catalyst (Amberlyst-15) results in clean epoxide hydrolysis to afford their corresponding terpene-anti-diols in good yields.

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.

Selective oxidation reactions of natural compounds with hydrogen peroxide mediated by methyltrioxorhenium

We have investigated the oxidative behaviour of natural compounds such as methyl abietate (1), farnesyl acetate (2), a-ionone (3), β-ionone (4), methyl linolelaidate (5), methyl linolenate (6) and bergamottin (7) with the oxidant system methyltrioxo-rhenium/ H2O2/pyridine. The reactions, performed in CH2Cl2/H2O at 25 °C, have shown good regioand stereoselectivity. The oxidation products were isolated by HPLC or silica gel chromatography and characterized by MS(EI), 1H-, 13C-NMR, APT, gCOSY, HSQC, TOCSY and NOESY measurements. The selectivity seems to be controlled by the nucleophilicity of double bonds and by stereoelectronic and steric effects.

Lipase-mediated synthesis of the enantiomeric forms of 4,5-epoxy4,5-dihydro-α-ionone, and 5,6-epoxy-5,6-dihydro-β-ionone. A new direct access to enantiopure (R)-, and (5)-α-ionone

Stereoselective lipase-mediated esterifications of epoxy-a-ionpl 5, and epoxy-ionol 9 afTorded suitable precursors of the enantiomers of the corresponding oxidised derivatives epoxy-u-ionone 3, and epoxy-ionone 4. An interesting development of this work is the easy conversion of enantiopure 3a, and 3b into highly valuable enantiopure (5)-, and (R)-ionone (1a, and Ib) via a mild deoxygenation reaction.

Diastereoface-selective epoxidations: Dependency on the reagent electrophilicity

Substrate-imposed steric constraints can be overriden by the pronounced preference of strong peracids for epoxidation on the π face, which has the highest electron density. For example, the sy:anti ratio for reaction (1) with CF3CO3H in CH2Cl2 is 82:18, that with CH3CO3H in toluene is 3:97.

A synthetic approach to (+/-)-forskolin. Part I. Preparation of key hydrobenzofuran intermediates

In a synthetic approach to (+/-)-forskolin 1, a stereoselective preparation of the unsaturated lactone 2 was envisaged.Propargylic derivatives 18a-c were prepared from available α-ionone 5 and treated with Bu3SnH/AIBN to give the bicyclic vinylstannanes 19a-c in high yield.From these compounds we then performed transmetallation reactions to obtain the 21a-c and 22b homologous derivatives.The two enyne compounds 29 and 30 were then prepared by our previous approach to lactone 2 involving a radical C7-C8 bond formation.In a second radical approach promoted by SmI2, the diol 10, was used to synthesize a potential precursor of the dialdehyde 9. - Keywords: forskolin; tributylstannane; radical cyclization; transmetallation; vinylstannane; vinyl iodide; Pd(0) coupling reaction

REACTIONS OF α-IONONE OXIDE WITH AMINIUM SALTS, BROENSTED AND LEWIS ACIDS. SYNTHESIS OF NEW TERMINAL GROUP SYNTHONS

Catalytic amounts of aminium salts induce the isomerization of α-ionone oxide, 5, affording 1,3,3-trimethyl-2-(3-oxo-1-buten-1-yl)cyclopent-1-ylcarbaldehydes, 6a,b together with trace amounts of 2,4,4-trimethyl-3-(3-oxo-1-buten-1-yl)cyclohexanones 6c,d.Pr

Optisch aktive 4,5-Epoxy-4,5-dihydro-α-ionone und Synthese der stereoisomeren 4,5:4',5'-Diepoxy-4,5,4',5'-tetrahydro-ε,ε-carotine und der sterische Verlauf ihrer Hydrolyse

We prove that epoxidation with peracid of α-ionone, contrary to a recently published statement, predominantly leads to the cis-epoxide.Acid hydrolysis affords a single 4,5-glycol whose structure, established by an X-ray analysis, shows that oxirane opening occured with inversion at the least substituted position (C(4)).Stable cis- and trans-epoxides are prepared by epoxidation of the C15-phosphonates derived from α-ionone.Both the racemic and optically active form are used for the synthesis of the 4,5:4',5'-diepoxy-4,5,4',5'-tetrahydro-ε,ε-carotenes having the following configuration in the end goups: meso-cis/cis, meso-trans/trans, rac-cis/trans, rac- and (6R,6'R)-cis/cis, rac- and (6R,6'R)-trans/trans, rac- and (6R,6'R)-cis/trans, and (6R,6'R)-cis/ε.Acid hydrolysis of the cis/cis-epoxycarotenoids under relatively strong conditions occurs again with inversion at C(4)/C(4') in case of the cis/cis-epoxycarotenoids, but at C(5)/C(5') in case of the trans/trans-epoxycarotenoids.An independent synthesis of this 4,5,4',5'-tetrahydro-ε,ε-carotene-4,5,4',5'-tetrol is presented.The irregular results of the oxirane hydrolysis are explained by assumption of neighbouring effects of the lateral chain. 400-MHz-1H-NMR data are given for each of the stereoisomeric sets.In the visible range of the CD spectra, the (6R,6R')-epoxycarotenoids compared with (6R,6R')-ε,ε-carotene exhibit an inversion of the Cotton effects.