Ozonolytic transformations of (S)-(−)-limonene

Ishmuratov, G. Yu.; Legostaeva, Yu. V.; Botsman, L. P.; Nasibullina, G. V.; Муслухов, Р. Р.; Казаков, Д. В.; Толстиков, Г. А.

doi:10.1134/s1070428012010034

Cited by 9 publications

(3 citation statements)

References 4 publications

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“…The syntheses of (4a S ,7 S )-4a-methyl-7-(prop-1-en-2-yl)-2,3,4,4a,5,6,7,8-octahydroquinolin-1-ium ( 1 ) and (4a S ,7 S )-1,4a-dimethyl-7-(prop-1-en-2-yl)decahydroquinolin-1-ium ( 2 ) have been previously reported. , The syntheses of (3 R ,6 R ,9a R )-6,9a-dimethyl-3-(prop-1-en-2-yl)decahydroquinolizin-5-ium ( 3 ) and (1 S ,8 S ,9a R )-1,9a-dimethyl-8-(prop-1-en-2-yl)decahydroquinolizin-5-ium ( 4 ) were accomplished in six and eight steps, respectively, starting from the known keto ester ( S )-methyl-6-oxo-3-(prop-1-en-2-yl)heptanoate, which was obtained by degradation of (−)-limonene. − The synthesis of 3 features a modified Curtius rearrangement that gives rise to the 3,6-dialkylated cyclic imine ( R )-6-methyl-3-(prop-1-en-2-yl)-2,3,4,5-tetrahydropyridine after acid-promoted cyclization . The latter was easily converted to the final (3 R ,6 R ,9a R )-trialkyl substituted quinolizidine 3 essentially as described by De Kimpe using MeMgBr .…”

Section: Methodsmentioning

confidence: 99%

Mechanistic Insights from the Binding of Substrate and Carbocation Intermediate Analogues to Aristolochene Synthase

et al. 2013

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Aristolochene synthase, a metal-dependent sesquiterpene cyclase from Aspergillus terreus, catalyzes the ionization-dependent cyclization of farnesyl diphosphate (FPP) to form the bicyclic eremophilane (+)-aristolochene with perfect structural and stereochemical precision. Here, we report the X-ray crystal structure of aristolochene synthase complexed with three Mg2+ ions and the unreactive substrate analogue farnesyl-S-thiolodiphosphate (FSPP), showing that the substrate diphosphate group is anchored by metal coordination and hydrogen bond interactions identical to those previously observed in the complex with three Mg2+ ions and inorganic pyrophosphate (PPi). Moreover, the binding conformation of FSPP directly mimics that expected for productively bound FPP, with the exception of the precise alignment of the C-S bond with regard to the C10-C11 π system that would be required for C1-C10 bond formation in the first step of catalysis. We also report crystal structures of aristolochene synthase complexed with Mg2+3-PPi and ammonium or iminium analogues of bicyclic carbocation intermediates proposed for the natural cyclization cascade. Various binding orientations are observed for these bicyclic analogues, and these orientations appear to be driven by favorable electrostatic interactions between the positively charged ammonium group of the analogue and the negatively charged PPi anion. Surprisingly, the active site is sufficiently flexible to accommodate analogues with partially or completely incorrect stereochemistry. Although this permissiveness in binding is unanticipated, based on the stereochemical precision of catalysis that leads exclusively to the (+)-aristolochene stereoisomer, it suggests the ability of the active site to enable controlled reorientation of intermediates during the cyclization cascade. Taken together, these structures illuminate important aspects of the catalytic mechanism.

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Section: Methodsmentioning

confidence: 99%

Mechanistic Insights from the Binding of Substrate and Carbocation Intermediate Analogues to Aristolochene Synthase

et al. 2013

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“…The similar result was obtained by us earlier for peroxide during the ozonolysis of S ‐limonene. [ 32 ] Thus, it is likely that α‐ketotrioxolane 8 under the action of pyridine rearranges according to the type of the Bayer–Villiger reaction, [ 33 ] leading to mixed anhydride 9 . Compounds 9 are converted to ketoaldehyde ester 4 (in MeOH) or to ketoaldehyde acid 10 (in CH 2 Cl 2 , after hydrolysis).…”

Section: Resultsmentioning

confidence: 99%

Ozonolytic transformations of (R)‐(−)‐carvon in the presence of pyridine

Myasoedova

Garifullina

Belyaeva

et al. 2022

J Chinese Chemical Soc

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Ozonolytic transformations of (R)‐(−)‐carvone in aprotic (CH2Cl2) and proton‐donor (MeOH) solvents in the presence of pyridine were carried out. A low conversion of the starting diene was noted when carrying out controlled ozonolysis by treatment with equivalent of О3. A mixture of 3‐acetyl‐5‐methoxy‐5‐oxopentanoic acid and methyl 4‐oxo‐3‐(2‐oxoethyl)pentanoate in MeOH and 5‐acetyl‐2‐methylcyclohex‐2‐en‐1‐one in CH2Cl2 were formed. Exhaustive ozonolysis of (R)‐(−)‐carvone in CH2Cl2 in the presence of pyridine leads to 3‐acetylpentadioic acid. The monomethyl ether of 3‐acetylpentadioic acid and the product of its cyclization—2,8‐dioxo‐1‐methylbicyclo[3.3.0]octane‐3,7‐dione were formed in MeOH/Py by the treatment of ozone excess.

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“…There are principles for the selection of suitable monomers and methods for modifying natural origin polymers in order to impart the desired properties. One of these substances is limonene [3][4][5]. Limonene is found in many essential oils and is an adaptable chemical raw material [6].…”

Section: Introductionmentioning

confidence: 99%

Renewable Polymers Derived from Limonene

et al. 2023

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Renewable natural and synthetic basic substances can be used to produce biodegradable polymers. Several methods of the polymerization of terpene limonene have been evaluated. The polymerization methods evaluated are radical polymerization, cationic polymerization and thiol-ene polymerization. The free-radical polymerization of limonene with azobisisobutyronitrile (AIBN) as an initiator was carried out. The cationic polymerization of limonene was carried out using AlCl3 as a catalyst. The copolymerization of limonene with mercaptoethanol, 2-mercaptoethyl ether without an initiator and with an AIBN initiator was studied and it was also shown that polymerization can proceed spontaneously. The resulting compounds were investigated by NMR and FTIR spectroscopy. The values of the molecular weight characteristics of the samples obtained are presented, such as: number-average molecular weight, hydrodynamic radius and characteristic viscosity, depending on the method of production. The coefficients α (molecular shape) in the Mark–Kuhn–Houwink equation are determined according to the established values of the characteristic viscosity. According to the values obtained, the AC molecules in solution have parameters α 0.14 to 0.26, which corresponds to a good solvent and the molecular shape-dense coil.

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Ozonolytic transformations of (S)-(−)-limonene

Cited by 9 publications

References 4 publications

Mechanistic Insights from the Binding of Substrate and Carbocation Intermediate Analogues to Aristolochene Synthase

Mechanistic Insights from the Binding of Substrate and Carbocation Intermediate Analogues to Aristolochene Synthase

Ozonolytic transformations of (R)‐(−)‐carvon in the presence of pyridine

Renewable Polymers Derived from Limonene

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