Liquid phase oxidation of α‐pinene. Influence of sodium hydroxide as additive

Martín, Juan Vicente González; Beltrán, Fernando J.; Frades, J.

doi:10.1002/jctb.280610412

Cited by 5 publications

(4 citation statements)

References 8 publications

(2 reference statements)

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“…[29][30][31][32][33][34] Oxyfunctionalization of cyclic olefins is of industrial and biological importance due to the possibility of transforming cheap and readily available substrates to valuable intermediates for fine chemicals and pharmaceutical synthesis. [35][36][37][38][39][40][41][42][43] a-Pinene is a standard molecule frequently used in ROA study. We chose epoxidation of a-pinene to a-pinene oxide and subsequent hydrolysis as an archetypal reaction.…”

Section: Introductionmentioning

confidence: 99%

Chirality transition in the epoxidation of (−)-α-pinene and successive hydrolysis studied by Raman optical activity and DFT

Qiu

Liu

et al. 2010

Phys. Chem. Chem. Phys.

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Characterization of the chirality evolution involved in chemical and biochemical reaction processes is extremely important to the understanding of the chiral catalysis mechanism. In this work, the chiral transition from the epoxidation of (-)-alpha-pinene to alpha-pinene oxide and successive hydrolysis to (-)-pinanediol has been studied as an archetype of the asymmetric catalysis by Raman optical activity (ROA) and the DFT calculation. Minor changes of the absolute configuration of the chiral products from (-)-alpha-pinene to (-)-pinanediol lead to the dramatic variation in ROA spectra indicating that the chirality is delocalized in the whole molecule rather than only concentrated on the chiral centers. The oxygen atom of alpha-pinene oxide contributes strong ROA signals while the two hydroxyl groups of (-)-pinanediol give no apparent contribution to the chirality in terms of ROA signals. Isolation of the two symmetric anisotropic invariants shows that the predominant contribution to the ROA signals stems from the electric dipole-magnetic dipole invariant, and the bond polarizability model is indeed found to be a good approximation for molecules composed of entirely axially-symmetric bonds in alpha-pinene oxide and (-)-pinanediol. This study demonstrates the feasibility of using ROA to sensitively monitor the variation of the chirality transition during the chiral reactions either in the chemical or biological system.

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Section: Introductionmentioning

confidence: 99%

Chirality transition in the epoxidation of (−)-α-pinene and successive hydrolysis studied by Raman optical activity and DFT

Qiu

Liu

et al. 2010

Phys. Chem. Chem. Phys.

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“…Furthermore, a Schenk rearrangement is a nondissociative mechanism (sigmatropic [2,3]-rearrangement ), therefore maintaining the ( E )-configuration of the first generated hydroperoxide. Verbenone 4 becomes more dominating at elevated temperature or at higher hydroperoxide concentrations at advanced autoxidation . Interestingly, in the presence of molecular oxygen and catalytic amounts of Co 2+ complexes at 80 °C the oxidation of verbenol 3 to verbenone 4 was successful in the case of ( E )-verbenol 3a , only, whereas ( Z )-verbenol 3b was assumed to further react to some rearrangement products.…”

Section: Resultsmentioning

confidence: 99%

Autoxidation versus Biotransformation of α-Pinene to Flavors with Pleurotus sapidus: Regioselective Hydroperoxidation of α-Pinene and Stereoselective Dehydrogenation of Verbenol

Krings¹,

Lehnert²,

Fraatz³

et al. 2009

J. Agric. Food Chem.

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The enzymatic conversion of alpha-pinene to verbenols, verbenone, and minor volatile flavors was studied using submerged cultured cells, lyophilisate, and microsomal fractions of the edible basidiomycete Pleurotus sapidus . The similarity of the product range obtained by the bioconversions with the range of products found after autoxidation of alpha-pinene at 100 degrees C suggested similar initial pinene radicals. Extracts of the bioconversions were analyzed using thin layer chromatography with hydroperoxide staining and cool on-column capillary gas chromatography-mass spectrometry. Two isomer alpha-pinene hydroperoxides were identified as the key intermediates and their structures confirmed by comparison with synthesized reference samples and by microchemical reduction to (Z)- and (E)-verbenol. When the biocatalysts were supplemented with one of the verbenols, only the (Z)-isomer was oxidized, indicating the activity of a highly stereospecific monoterpenol dehydrogenase. The structural comparison of subunits shows that fungal oxifunctionalization reactions of some common terpene substrates, such as (+)-limonene or (+)-valencene, might likewise be catalyzed by dioxygenases rather than by CYP450 enzymes, as previously assumed.

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“…The oxidation of the cis-and trans-pinanes 345 by in situ generated RuO, has been studied,502 as has the oxidation of a-pinene 336 using molecular oxygen as oxidant in the presence of Fe3+ or Mn3' phthalo~yanines.~~~ The oxidation of neat a-pinene 336 by oxygen in the presence of (4-MePy),CoBr2 yields verbenone (339).504 Ozone can act as an initiating agent for the liquid phase oxidation of a-pinene 336,505 and the effect of the partial pressure of ozone upon this process has been examined. 506 The addition of NaOH to the system retards the reaction, but increases the selectivity for the production of verbenol 338 and verbenone 339. 507 P-Pinene 337 reacts with the enone 354, generated in situ, to give the hetero-Diels-Alder adduct 355.…”

Section: Pinanesmentioning

confidence: 99%

“…506 The addition of NaOH to the system retards the reaction, but increases the selectivity for the production of verbenol 338 and verbenone 339. 507 P-Pinene 337 reacts with the enone 354, generated in situ, to give the hetero-Diels-Alder adduct 355. 516 Treatment of P-pinene 337 with PCl, leads to a mixture of both 356 and 357.…”

Section: Pinanesmentioning

confidence: 99%

Monoterpenoids

Grayson¹

1997

Nat. Prod. Rep.

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Liquid phase oxidation of α‐pinene. Influence of sodium hydroxide as additive

Cited by 5 publications

References 8 publications

Chirality transition in the epoxidation of (−)-α-pinene and successive hydrolysis studied by Raman optical activity and DFT

Chirality transition in the epoxidation of (−)-α-pinene and successive hydrolysis studied by Raman optical activity and DFT

Autoxidation versus Biotransformation of α-Pinene to Flavors with Pleurotus sapidus: Regioselective Hydroperoxidation of α-Pinene and Stereoselective Dehydrogenation of Verbenol

Monoterpenoids

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