1197-06-4Relevant articles and documents
Pauson-Khand Reactions with Concomitant C?O Bond Cleavage for the Preparation of 5,5- 5,6- and 5,7-Bicyclic Ring Systems
Ma, Ding,Hu, Naifeng,Ao, Junli,Zang, Shaoli,Yu, Guo,Liang, Guangxin
, p. 1887 - 1891 (2021)
Pauson-Khand reactions (PKR) with concomitant C?O bond cleavage have been developed for construction of 5,5- 5,6- and 5,7-bicyclic ring systems bearing complex stereochemistry. The chemistry generates intermolecular PKR-type products in an absolute regio- and stereochemical control which is hardly achievable through real intermolecular Pauson-Khand reactions. A mechanism for this Pauson-Khand reaction has been proposed based on deuterium labelling experiments. (Figure presented.).
Sex differences in the metabolism of (+)- and (-)-limonene enantiomers to carveol and perillyl alcohol derivatives by cytochrome P450 enzymes in rat liver microsomes
Miyazawa, Mitsuo,Shindo, Masaki,Shimada, Tsutomu
, p. 15 - 20 (2002)
(+)-Limonene is reported to cause nephropathy in male rats, but not in female rats and other species of animals including mice, rabbits, guinea pigs, and dogs. Male rats contain high levels of α2u-globulin in kidneys, and it has been shown that limonene a
Comparative anticonvulsant study of epoxycarvone stereoisomers
Salgado, Paula Regina Rodrigues,Da Fonsêca, Diogo Vilar,Braga, Renan Marinho,De Melo, Cynthia Germoglio Farias,Andrade, Luciana Nalone,De Almeida, Reinaldo Nóbrega,De Sousa, Dami?o Pergentino
, p. 19660 - 19673 (2015)
Stereoisomers of the monoterpene epoxycarvone (EC), namely (+)-cis-EC, (-)-cis-EC, (+)-Trans-EC, and (-)-Trans-EC, were comparatively evaluated for anticonvulsant activity in specific methodologies. In the pentylenetetrazole (PTZ)-induced anticonvulsant test, all of the stereoisomers (at 300 mg/kg) increased the latency to seizure onset, and afforded 100% protection against the death of the animals. In the maximal electroshock-induced seizures (MES) test, prevention of tonic seizures was also verified for all of the isomers tested. However, the isomeric forms (+) and (-)-Trans-EC showed 25% and 12.5% inhibition of convulsions, respectively. In the pilocarpine-induced seizures test, all stereoisomers demonstrated an anticonvulsant profile, yet the stereoisomers (+) and (-)-Trans-EC (at 300 mg/kg) showed a more pronounced effect. A strychnine-induced anticonvulsant test was performed, and none of the stereoisomers significantly increased the latency to onset of convulsions; the stereoisomers probably do not act in this pathway. However, the stereoisomers (+)-cis-EC and (+)-Trans-EC greatly increased the latency to death of the animals, thus presenting some protection. The four EC stereoisomers show promise for anticonvulsant activity, an effect emphasized in the isomers (+)-cis-EC, (+)-Trans-EC, and (-)-Trans-EC for certain parameters of the tested methodologies. These results serve as support for further research and development of antiepileptic drugs from monoterpenes.
New orthogonally functionalized synthetic blocks from R-(-)-carvone
Valeev,Khasanova,Miftakhov
, p. 670 - 673 (2010)
The intramolecular cyclization of (-)-cis-carveol under iodine treatment afforded (1R,5R,6S)-6-iodomethyl-2,6-dimethyl-7-oxabicyclo[3.2.1]oct-2-ene that was subjected to allyl oxydation with the complex CrO3DMP giving a synthetically valuable building block, (1R,5R,6S)-6-iodomethyl-2,6-dimethyl-7- oxabicyclo[3.2.1]oct-2-ene-4-one. In the latter the double bond was cleaved by ozonization to obtain the expected trioxo derivative, and the subsequent ozonolysis of its enol form provided a multiple functionalized tetrahydrofuran derivative. Pleiades Publishing, Ltd., 2010.
Synthesis and properties of novel chiral imidazolium-based ionic liquids derived from carvone
Santamarta, Francisco,Vilas, Miguel,Tojo, Emilia,Fall, Yagamare
, p. 31177 - 31180 (2016)
A large series of novel chiral imidazolium ionic liquids were synthesized using the terpenoid carvone as the chiral substrate. Their specific rotations were characterized and their potential use in chiral recognition was demonstrated by studying interactions with racemic Mosher's acid salt.
Chiral building blocks from R-(-)-carvone: N-bromosuccinimidemediated addition-sceletal rearrangement of (-)-cis-carveol
Valeev, Ruslan F.,Selezneva, Nataliya K.,Starikova, Zoya A.,Pankrat'ev, Evgenii Yu.,Miftakhov, Mansur S.
, p. 77 - 79 (2010)
Synthetically valuable bicyclic blocks 5, 7 and 9 were prepared by the oxidative cleavage of the double bond of 4 with the RuCl3-NaIO4 system and O3.
Stereoselective metabolism of the monoterpene carvone by rat and human liver microsomes
Jaeger, Walter,Mayer, Marion,Platzer, Peter,Reznicek, Gottfried,Dietrich, Hermann,Buchbauer, Gerhard
, p. 191 - 197 (2000)
The large amounts of carvone enantiomers consumed as food additives and in dental formulations justifies the evaluation of their biotransformation pathway. The in-vitro metabolism of R-(-)- and S-(+)-carvone was studied in rat and human liver microsomes using chiral gas chromatography. Stereoselective biotransformation was observed when each enantiomer was incubated separately with liver microsomes. 4R, 6S-(-)-Carveol was NADPH-dependently formed from R-(-)-carvone, whereas 4S, 6S-(+)-carveol was produced from S-(+)-carvone. Metabolite formation followed Michaelis-Menten kinetics exhibiting a significant lower apparent K(m) (Michaelis-Menten Constant) for 4R, 6S-(-)-carveol compared with 4S, 6S-(+)-carveol in rat and human liver microsomes (28.4±10.6 μM and 69.4±10.3 μM vs 33.6±8.5 μM and 98.3±22.4 μM). The maximal formation rate (V(max)) determined in the same microsomal preparations yielded 30.2±5.0 and 32.3±3.9 pmol (mg protein)-1 min-1 in rat liver and 55.3±5.7 and 65.2±4.3 pmol (mg protein)-1 min-1 in human liver microsomes. Phase II conjugation of the carveol isomers by rat and human liver microsomes in the presence of UDPGA (uridine S'-diphosphogluaronic acid) only revealed glucuronidation of 4R, 6S-(-)-carveol. V(max) for glucuronide formation was more than 4-fold higher in the rat liver compared with human liver preparations (185.9±34.5 and 42.6±7.1 pmol (mg protein)-1 min-1, respectively). K(m) values, however, showed no species-related difference (13.9±4.1 μM and 10.2±2.2 μM). This study demonstrated stereoselectivity in phase-I and phase-II metabolism for R-(-)- and S-(+)-carvone and might be predictive for carvone biotransformation in man.
Percutaneous absorption of the montoterperne carvone: implication of stereoselective metabolism on blood levels.
Jaeger,Mayer,Reznicek,Buchbauer
, p. 637 - 642 (2001)
The purpose of this study was to determine whether an enantioselective difference in the metabolism of topically applied R-(-)- and S-(+)-carvone could be observed in man. In a previous investigation we found that R-(-)- and S-(+)-carvone are stereoselectively biotransformed by human liver microsomes to 4R,6S-(-)- and 45,6S-(+)-carveol, respectively, and 4R,6S-(-)-carveol is further glucuronidated. We therefore investigated the metabolism and pharmacokinetics of R-(-)- and S-(+)-carvone in four healthy subjects using chiral gas chromatography as the analytical method. Following separate topical applications at a dose of 300 mg, R-(-)- and S-(+)-carvone were rapidly absorbed, resulting in significantly higher Cmax levels for S-(+)-carvone (88.0 vs 23.9 ng mL(-1)) and longer distribution half-lives (t(1/2alpha)) (19.4 vs 7.8 min), resulting in 3.4-fold higher areas under the blood concentration-time curves (5420 vs 1611 ng min mL(-1)). The biotransformation products for both enantiomers in plasma were below detection limit. Analysis of control- and beta-glucuronidase pretreated urine samples, however, revealed a stereoselective metabolism of R-(-)-carvone to 4R,6S-(-)-carveol and 4R,6S-(-)-carveol glucuronide. No metabolites could be found in urine samples after S-(+)-carvone application. These data indicate that stereoselectivity in phase-I and phase-II metabolism has significant effects on R-(-)- and S-(+)-carvone pharmacokinetics. This might serve to explain the increased blood levels of S-(+)-carvone.
Biotransformation of (S)-(-)- and (R)-(+)-limonene using Solanum aviculare and Dioscorea deltoidea plant cells
Vanek, Tomas,Valterova, Irena,Vaisar, Tomas
, p. 1347 - 1351 (1999)
(S)-(-)- and (R)-(+)-limonene was transformed to carvone via corresponding cis- and trans-carveol using Solanum aviculare and Dioscorea deltoidea plant cells. Both carveols and carvone formed were racemic in all biotransformations.
Modelling the biokinetic resolution of diastereomers present in unequal initial amounts
De Carvalho, Carla C.C.R.,Van Keulen, Frederik,Da Fonseca, M.Manuela R.
, p. 1637 - 1643 (2002)
The enantiomeric ratio (E) is commonly used to evaluate enzyme-catalysed kinetic resolutions. Chen et al. (1982) proposed a model for the enantiomeric ratio, which relates the extent of substrate conversion and the enantiomeric excess. The model, however,
