(1<i>R</i>,5<i>S</i>)-(+)-Nopinone of High Enantiomeric Purity

Kozmina, N.; Paquette, Leo A.

doi:10.1080/00397919608003558

Cited by 10 publications

(5 citation statements)

References 3 publications

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“…GC‐FID analyses of the myrcene and ocimene samples introduced into the chamber showed the presence of impurities of ∼10% in the myrcene and ∼5% in the ocimene; however, these impurities did not interfere because they were essentially unreactive. 4‐Vinyl‐4‐pentenal was synthesized by ozonizing myrcene as described by Kozmina and Paquette [1996]. Methyl nitrite was synthesized as described by Taylor et al [1980] and was stored at 77 K under vacuum.…”

Section: Experimental Methodsmentioning

confidence: 99%

Products of the OH radical‐ and O₃‐initiated reactions of myrcene and ocimene

et al. 2002

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[1] We have investigated products formed from the gas-phase reactions of OH radicals and O 3 (at 296 ± 2 K and 740 Torr total pressure of purified air) with the biogenic organic compounds myrcene and ocimene, using gas chromatographic analyses. In addition to the formation of acetone the OH radical reaction with myrcene in the presence of NO resulted in the formation of 4-vinyl-4-pentenal in 19 ± 4% yield, while the corresponding ocimene reaction showed no formation of the analogous product 4-methyl-3, 5-hexadienal (<2% yield). The O 3 reactions with myrcene and ocimene in the presence of an OH radical scavenger formed acetone (21 ± 3%) and 4-vinyl-4-pentenal (70 ± 13%) from myrene, and acetone (24 ± 4%) and 4-methyl-3,5-hexadienal (33 ± 6%) from ocimene. Reaction pathways leading to these products are discussed.

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Section: Experimental Methodsmentioning

confidence: 99%

Products of the OH radical‐ and O₃‐initiated reactions of myrcene and ocimene

et al. 2002

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“…Remarkably, these crystals were found (Garner, 1986) to be centrosymmetric (racemic), despite the �-pinene being of 92% ee. This suggests that the enantiomeric purity of this allylmetallic can be improved simply by partial crystallization, though this has also been accomplished for �-pinene by crystallization of the silver perchlorate complex (Kozmina & Paquette, 2006). Despite several attempts, crystals obtained from more extensive crystallization [presumably consisting of only the (À )-enantiomer] (Sheldrick, 2008) and FinalCif (D. Kratzert, https://dkratzert.de/finalcif.html).…”

Section: Resultsmentioning

confidence: 99%

Preferential crystallization of (±)-pinenyllithium·TMEDA

Erickson,

Haltiwanger,

Rahim

et al. 2024

Acta Crystallogr C

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(±)-Pinenyllithium·TMEDA or (tetramethylethylenediamine-κ2 N,N′)(η3-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptyl)lithium, [Li(C10H15)(C6H16N2)], is readily prepared from β-pinene, butyllithium and TMEDA, and the racemic material preferentially crystallizes even from 96:4 (92% ee) mixtures of (−)- and (+)-β-pinene, respectively. The structure is monomeric, with the geminal-dimethyl bridge of the bicyclic structure shielding one face of the allyl system, restricting the lithium to the opposite face and preventing the Li–allyl–Li aggregation observed with some other allyllithium systems. The symmetry of the allyl system, bond lengths, bond angles and out-of-plane deviations are compared to existing structures. In addition, a much older structure of this complex is compared to this very recent one.

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“…Two methods have so far been disclosed. Complexation of 2 with AgClO 4 resulted in an adduct with 2:1 molar composition 79,88. Identical pinene enantiomers are preferentially incorporated in the complex, so careful removal of excess 2 by vacuum distillation at room temperature allowed for purification of the complex.…”

Section: Synthesis By Ozonolysis Of β‐Pinenementioning

confidence: 99%

“…Identical pinene enantiomers are preferentially incorporated in the complex, so careful removal of excess 2 by vacuum distillation at room temperature allowed for purification of the complex. Hydrolysis of the white precipitate afforded 2 with α D 21 = –22.5 (initially –19.9) 79. However, handling of the complex is critical because of its shock sensitivity (initiation temperature <65 °C).…”

Section: Synthesis By Ozonolysis Of β‐Pinenementioning

confidence: 99%

Synthesis of Nopinone from β‐Pinene – A Journey Revisiting Methods for Oxidative Cleavage of C=C Bonds in Terpenoid Chemistry

Stolle

2013

Eur J Org Chem

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The easily accessible 2‐(methylamino)pyridinato titanium complex initially synthesized by Kempe is used as catalyst for efficient intramolecular hydroaminoalkylation reactions of secondary aminoalkenes. The corresponding reactions of N‐aryl‐substituted 1‐aminohept‐6‐enes and 1‐aminohex‐5‐enes directly give access to 2‐methylcyclohexyl‐ or 2‐methylcyclopentylamines in good yields. In addition, intramolecular hydroaminoalkylations of an N‐alkyl‐substituted secondary aminoalkene and a geminally β‐disubstituted substrate are described for the first time. While all products are formed as mixtures of two diastereoisomers, better trans/cis ratios are observed during the formation of 2‐methylcylopentylamines.

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(1R,5S)-(+)-Nopinone of High Enantiomeric Purity

Cited by 10 publications

References 3 publications

Products of the OH radical‐ and O₃‐initiated reactions of myrcene and ocimene

Products of the OH radical‐ and O₃‐initiated reactions of myrcene and ocimene

Preferential crystallization of (±)-pinenyllithium·TMEDA

Synthesis of Nopinone from β‐Pinene – A Journey Revisiting Methods for Oxidative Cleavage of C=C Bonds in Terpenoid Chemistry

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(1R,5S)-(+)-Nopinone of High Enantiomeric Purity

Cited by 10 publications

References 3 publications

Products of the OH radical‐ and O3‐initiated reactions of myrcene and ocimene

Products of the OH radical‐ and O3‐initiated reactions of myrcene and ocimene

Preferential crystallization of (±)-pinenyllithium·TMEDA

Synthesis of Nopinone from β‐Pinene – A Journey Revisiting Methods for Oxidative Cleavage of C=C Bonds in Terpenoid Chemistry

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Products of the OH radical‐ and O₃‐initiated reactions of myrcene and ocimene

Products of the OH radical‐ and O₃‐initiated reactions of myrcene and ocimene