Autoxidation of α-Pinene<sup>2</sup>

Moore, Richard N.; Golumbic, Calvin; Fisher, G. S.

doi:10.1021/ja01587a022

Cited by 61 publications

(29 citation statements)

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“…Decomposition was suppressed with increasing alkalinity of the incubation buffer; the compound was stable for several hours in 0.1 M glycine-NaOH buffer (pH 9). These observations were compatible with the reported pH-dependent stability profile of a-pinene oxide under rather different conditions (13,15). Initial biochemical studies were therefore performed in 0.1 M glycine-NaOH buffer to suppress nonenzymic transformation.…”

Section: Resultssupporting

confidence: 86%

Bacterial metabolism of alpha-pinene: pathway from alpha-pinene oxide to acyclic metabolites in Nocardia sp. strain P18.3

et al. 1987

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Over 20 gram-positive bacteria were isolated by elective culture with (-+)-a-pinene as the sole carbon source. One of these strains, Nocardia sp. strain P18.3, was selected for detailed study. c-Pinene-grown cells oxidized, without lag, a-pinene, ot-pinene oxide (epoxide), and the cis and trans isomers of 2-methyl-5-isopropylhexa-2, 5-dienal (16,17) is indicative of the second ring cleavage occurring between carbon atoms 2 and 3 of the a.-pinene. In contrast, accumulation of the cis isomer of 2-methyl-5-isopropylhexa-2,5-dienoic acid by Pseudomonas putida PX1 (9, 10) and the trans isomer of the same compound by a mutant of P. putida PIN11 (19) is indicative of the second ring cleavage occurring between carbon atoms 3 and 4 (Fig. 1).With the exception of some whole cell oxidation studies and limited characterization of perillaldehyde and perillyl alcohol dehydrogenases from a-pinene-grown Pseudomonas sp. strain PL (2,16,17), the pathways proposed for cleavage of a-pinene have not been substantiated at the subcellular level.In a recent short communication (Floyd et al., EMBO Workshop) a strain of Pseudomonas fluorescens was reported to catalyze the NADH-linked oxygenation of a-pinene to form the epoxide (a-pinene oxide), and then cleavage of both rings of the epoxide by a decyclase with the formation of a novel aldehyde.

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Section: Resultssupporting

confidence: 86%

Bacterial metabolism of alpha-pinene: pathway from alpha-pinene oxide to acyclic metabolites in Nocardia sp. strain P18.3

et al. 1987

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“…The barrier of such a thermoneutral reaction is computed to be slightly higher than for Equation (18), that is, 4.8 kcal mol À1 for the model reaction CH 3 OO · +CH 3 OOH, leading to a k 19 (363 K) % 4 10 5 m À1 s À1 . Therefore this reaction can compete with the allylic H abstractions and C=C addition reactions, even at very low hydroperoxide concentrations.…”

Section: Chemo-selectivity and Interconversion Of Peroxyl Radicalsmentioning

confidence: 91%

“…[17] Despite its industrial and academic interest, the basic chemistry behind the oxidation process is not well understood. [18,19] The biotechnological oxidation of a-pinene has also been investigated, but continues to be a challenging task, owing to the long reaction time. [20] A detailed understanding of the molecular mechanisms of autoxidation conditions would not only be useful for optimizing reaction parameters and designing appropriate catalysts, [21][22][23][24][25][26] but could also inspire a broadening of the scope of the autoxidation substrate.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the Aerobic Oxidation of α‐Pinene

2010

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A combined experimental and theoretical approach is used to study the thermal autoxidation of α‐pinene. Four different types of peroxyl radicals are generated; the verbenyl peroxyl radical being the most abundant one. The peroxyl radicals propagate a long radical chain, implying that chain termination does not play an important role in the production of the products. Two distinct types of propagation steps are active in parallel: the abstraction of allylic H atoms and the addition to the unsaturated CC bond. The efficiency for both pathways appears to depend on the structure of the peroxyl radical. The latter step yields the corresponding epoxide product, as well as alkoxyl radicals. Under the investigated reaction conditions the alkoxyl radicals seem to produce both the alcohol and ketone products, the ketone presumably being formed upon the abstraction of the weakly bonded αH atom by O2. This mechanism explains the predominantly primary nature of all quantified products. At higher conversion, co‐oxidation of the hydroperoxide products constitutes an additional, albeit small, source of alcohol and ketone products.

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“…Verbenone (and verbenol) can be generated through autoxidation of host-released α-pinene coming into contact with atmospheric oxygen (Hunt et al, 1989;Moore et al, 1956). Microbes including bark beetle symbionts and incidental associates are also capable of oxidizing α-pinene to verbenol and/or verbenol to verbenone Brand et al, 1975;Hunt and Borden, 1990;Xu et al, 2015).…”

Section: Verbenonementioning

confidence: 99%

Semiochemicals in the Natural History of Southern Pine Beetle Dendroctonus frontalis Zimmermann and Their Role in Pest Management

Sullivan

2016

Advances in Insect Physiology

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Autoxidation of α-Pinene²

Cited by 61 publications

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Bacterial metabolism of alpha-pinene: pathway from alpha-pinene oxide to acyclic metabolites in Nocardia sp. strain P18.3

Bacterial metabolism of alpha-pinene: pathway from alpha-pinene oxide to acyclic metabolites in Nocardia sp. strain P18.3

Mechanism of the Aerobic Oxidation of α‐Pinene

Semiochemicals in the Natural History of Southern Pine Beetle Dendroctonus frontalis Zimmermann and Their Role in Pest Management

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Autoxidation of α-Pinene2

Cited by 61 publications

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Bacterial metabolism of alpha-pinene: pathway from alpha-pinene oxide to acyclic metabolites in Nocardia sp. strain P18.3

Bacterial metabolism of alpha-pinene: pathway from alpha-pinene oxide to acyclic metabolites in Nocardia sp. strain P18.3

Mechanism of the Aerobic Oxidation of α‐Pinene

Semiochemicals in the Natural History of Southern Pine Beetle Dendroctonus frontalis Zimmermann and Their Role in Pest Management

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Autoxidation of α-Pinene²