103475-43-0

Upstream product

• 87-44-5 β-caryophyllene 
• 61824-50-8 (Z)-(1R,9S)-4,11,11-Trimethyl-8-methylene-bicyclo[7.2.0]undec-3-en-5-one 
• 87-44-5 β-caryophyllene 
• 64-19-7 acetic acid 
• 3691-12-1 (1S,4S,7R)-7-Isopropenyl-1,4-dimethyl-1,2,3,4,5,6,7,8-octahydro-azulene 

Downstream Products

• 2649-64-1 clovanediol 
• 155485-76-0 (β,9β)-caryolane-1,9-diol 
• 92760-17-3 (1R,5S,8R,9R)-4,4,8-trimethylbicyclo<6.3.1.0^1,5>dodeca-2-en-9-ol 
• 122571-87-3 (1R,2S,5R,8S,9S)-1,4,4,8-tetramethyltricyclo[6.3.0.0^2,5]undec-9-yl acetate 
• 86834-01-7 4,5-dihydrocaryophyllen-4β-ol 
• 92174-64-6 Acetic acid (1S,5S,6S,9R)-6,10,10-trimethyl-2-methylene-bicyclo[7.2.0]undec-5-yl ester 
• 92174-64-6 1R,4R,5S,9S-4,5-dihydrocaryophyllen-5-ol acetate 
• 99881-55-7 1R,5R,9S-5-acetoxy-11,11-dimethyl-4,8-bismethylenebicyclo<7.2.0>undecane 
• 1213270-03-1 C₂₁H₂₉BrO₂ 
• 19431-76-6 caryophyllenol-II 
• 32214-91-8 Acetic acid (Z)-(1R,5R,9S)-4,11,11-trimethyl-8-methylene-bicyclo[7.2.0]undec-3-en-5-yl ester 
• 88514-10-7 ((1S,8R)-4,10,10-Trimethyl-7-methylene-bicyclo[6.2.0]dec-4-yl)-methanol 
• 19431-76-6 caryophyllenol-I 
• 19431-79-9 (1S,5S,9R)-10,10-Dimethyl-2,6-dimethylene-bicyclo[7.2.0]undecan-5-ol 

Relevant academic research and scientific papers

Thermoconversion of caryophyllene- to farnesene-type sesquiterpenes. Short access to the enantiomers of (6RS,7RS)- and (6RS,7SR)-6,7-epoxy-6,7-dihydro-β-farnesenes

Flash-vacuum thermolysis of the four diastereoisomeric 5,6-epoxy-5,6-dihydro-caryophyllenes 1-4 at 500-550°/0.1-0.7 Torr leads to the hitherto unreported enantiomers of (6RS,7RS)- and (6RS,7SR)-6,7-epoxy-6,7-dihydro-β-farnesenes ((±)-5 and (±)-6, resp.). In particular, (+)-5 is formed in 45% yield (ca. 90% ee) and is, thus, an attractive chiral building block for natural-product synthesis.

Ionic liquid-mediated catalytic oxidation of β-caryophyllene by ultrathin 2D metal-organic framework nanosheets under 1 atm O2

An ionic liquid (IL)-mediated facile method was established for the epoxidation of β-caryophyllene with molecular oxygen using ultrathin (～3?6 nm) 2D Cu-, Co- or Ce-based MOF nanosheets. Under the optimum conditions, high selectivity (92.4percent) and excellent yield (86.7percent) for β-caryophyllene epoxide were obtained over ultrathin (～5.5 nm) Cu-TCPP nanosheets (TCPP = tetrakis(4-carboxyphenyl)porphyrin) with the aid of [C12mim]Cl at 313 K and 1 atm O2. Notably, a small amount of [C12mim]Cl (1-dodecyl-3-methylimidazolium chloride, 5.0 mol percent) played pivotal roles in forming a favorable microenvironment in-situ, thus significantly improving the catalytic performances of above-mentioned Cu-TCPP nanosheets containing PVP stabilizer. Moreover, ultrathin Cu-TCPP nanosheets showed better stability during β-caryophyllene transformation in the presence of amphiphilic [C12mim]Cl, as supported by TEM and XRD analyses. Importantly, the addition of TBHP (tert-butyl hydroperoxide, 13.0 mol percent) initiator is also crucial for the aerobic oxidation of β-caryophyllene via Cu-TCPP nanosheets/[C12mim]Cl/TBHP/O2 nanosystem. Further insights into the synergistic effects and free radical mechanism were achieved by fluorescence, DRUV-Vis, UV-vis and XPS measurements.

Chromium(III) terephthalate metal organic framework (MIL-101): Hf-free synthesis, structure, polyoxometalate composites, and catalytic properties

Hybrid materials of the metal-organic framework (MOF), chromium(III) terephthalate (MIL-101), and phosphotungstic acid (PTA) were synthesized in aqueous media in the absence of hydrofluoric acid. XRD analysis of the MIL101/PTA composites indicates the presence of ordered PTA assemblies residing in both the large cages and small pores of MIL-101, which suggests the formation of previously undocumented structures. The MIL101/PTA structure enables a PTA payload 1.5-2 times higher than previously achieved. The catalytic performance of the MIL101/PTA composites was assessed in the Baeyer condensation of benzaldehyde and 2-naphthol, in the three-component condensation of benzaldehyde, 2-naphthol, and acetamide, and in the epoxidation of caryophyllene by hydrogen peroxide. The catalytic efficiency was demonstrated by the high (over 80-90%) conversion of the reactants under microwave-assisted heating. In four consecutive reaction cycles, the catalyst recovery was in excess of 75%, whereas the product yields were maintained above 92%. The simplicity of preparation, exceptional stability, and reactivity of the novel composites indicate potential in utilization of these catalytic matrices in a multitude of catalytic reactions and engineering processes.

Transannular cyclization of epoxycaryophyllenes catalyzed by Ti III: An efficient synthesis of tricyclo[6.3.0.02,5] undecanes

The transannular cyclization of epoxycaryophyllenes 2-7 catalyzed by TiIII has been investigated. This cyclization led to alcohols 8-15, all of them possessing a tricyclo[6.3.0.02,5]undecane skeleton. All of these compounds present pleasant aromatic properties. The cyclization takes place with high yields (> 80 %) and via the αα or ββ conformation of the intermediate radical I. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Stereochemistry of 14-hydroxy-β-caryophyllene and related compounds

The isomerization of β-caryophyllene (3), under treatment with SeO2, is described. Chemical correlations, between 3 and 14-hydroxy-β-caryophyllene (6) from Juniperus oxycedrus, are established. High resolution 1H NMR spectra and analysis by molecular mechanics of 3, 6 and 14-acetoxy-β-caryophyllene (7) indicate the existence of two conformational isomers, βα and ββ, in each compound. At 25°C, the βα conformer predominates in 3 and 7 but the ββ conformer predominates in 6. The higher percentage of 6ββ possibly derives from an intramolecular hydrogen bond. The treatment of 3, 6 and 7 with m-CPBA generates, in each case, two diastereomeric 4,5-epoxi-derivatives. The epoxides obtained from 6 have been isolated and analysed separately.

A further step to sustainable palladium catalyzed oxidation: Allylic oxidation of alkenes in green solvents

The palladium catalyzed oxidation of alkenes with molecular oxygen is a synthetically important reaction which employs palladium catalysts in solution; therefore, a solvent plays a critical role for the process. In this study, we have tested several green solvents as a reaction medium for the allylic oxidation of a series of alkenes. Dimethylcarbonate, methyl isobutyl ketone, and propylene carbonate, solvents with impressive sustainability ranks and very scarcely exploited in palladium catalyzed oxidations, were proved to be excellent alternatives for the solvents conventionally employed in these processes, such as acetic acid. Palladium acetate alone or in the combination with p-benzoquinone efficiently operates as the catalyst for the oxidation of alkenes by dioxygen under 5–10 atm. For most substrates, the systems in green solvents showed better selectivity for allylic oxidation products as compared to pure acetic acid; moreover, the reactions in propylene carbonate solutions occurred even faster than in acetic acid.

An ultrathin amino-acid based copper(II) coordination polymer nanosheet for efficient epoxidation of β-caryophyllene

Natural amino acids are important building blocks for the construction of intriguing coordination polymers (CPs) because of their abundance, inexpensiveness and environmental benignness. Herein, two copper(II) CPs, namely, 2D CuIle-e nanosheet (e: ethanol) and 1D CuIle-m nanoshuttle (m: methanol), were fabricated from L-isoleucine (Ile) and well characterized with single-crystal x-ray diffraction, XPS spectra, TEM and AFM, etc. More importantly, two novel and stable catalytic nanosystems, i.e. CuIle-e/acetone/TBHP (tert-butyl hydroperoxide) and CuIle-e/THF/O2/TBHP, were thus conveniently built by using ultrathin 2D CuIle-e nanosheet (~ 2.3 nm) in suitable aprotic solvents. Under mild conditions, complete conversion of β-caryophyllene and good yields (86.1% or 87.2%) for β-caryophyllene epoxide were gained via CuIle-e/acetone/TBHP or CuIle-e/THF/O2 (1 atm)/TBHP (10.0 mol%), respectively. Notably, ultrathin CuIle-e nanosheet showed fairly satisfactory stability, which may open a unique window for the facile fabrication of new amino-acid based CP nanosystems with outstanding catalytic performances in actual applications.

Electron transfer-initiated epoxidation and isomerization chain reactions of β-caryophyllene

The abundant sesquiterpene b-caryophyllene can be epoxidized by molecular oxygen in the absence of any catalyst. In polar aprotic solvents, the reaction proceeds smoothly with epoxide selectivities exceeding 70%. A mechanistic study has been performed and the possible involvement of free radical, spin inversion, and electron transfer mechanisms is evaluated using experimental and computational methods. The experimental data-including a detailed reaction product analysis, studies on reaction parameters, solvent effects, additives and an electrochemical investigation-all support that the spontaneous epoxidation of b-caryophyllene constitutes a rare case of unsensitized electron transfer from an olefin to triplet oxygen under mild conditions (80 8C, 1 bar O2). As initiation of the oxygenation reaction, the formation of a caryophyllene-derived radical cation via electron transfer is proposed. This radical cation reacts with triplet oxygen to a dioxetane via a chain mechanism with chain lengths exceeding 100 under optimized conditions. The dioxetane then acts as an in situ-formed epoxidizing agent. Under nitrogen atmosphere, the presence of a one-electron acceptor leads to the selective isomerization of b -caryophyllene to isocaryophyllene. Observations indicate that this isomerization reaction is a novel and elegant synthetic pathway to isocaryophyllene.

1-HYDROXY-OCTAHYDROAZULENES AS FRAGRANCES

(3S,5R)-3,8-dimethyl-5-(prop-1-en-2-yl)-octahydroazulen-1-ols, their use as flavour or fragrance ingredient, and a process of their production by oxidation in the presence of laccase.

An effective synthesis of acid-sensitive epoxides via oxidation of terpenes and styrenes using hydrogen peroxide under organic solvent-free conditions

An efficient epoxidation process for various terpenes and styrenes using a hydrogen peroxide-tungsten catalytic system with organic solvent-and halide-free conditions was developed. In the presence of the catalytic system, Na 2WO4, PhP(O)(OH)2, and [Me(n-C 8H17)3N]HSO4, and under weak acidic conditions, hydrogen peroxide successfully epoxidized -pinene to -pinene oxide in 95% selectivity at 91% conversion, while the previously published conditions utilizing NH2CH2P(O)(OH)2 as a promoter provided no epoxide. Georg Thieme Verlag Stuttgart.