Rearrangement of linalool, geraniol, nerol and their derivatives

Cori, Osvaldo; Chayet, L.; Pérez, Luz; Bunton, Clifford A.; Hachey, David L.

doi:10.1021/jo00358a028

Cited by 35 publications

(32 citation statements)

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“…Actually, 10 days is too long to be able to identify the different intermediate products of reaction. Cori et al studied the kinetics of those reactions and concluded that the hydration of the linalyl carbocation in linalool is faster than the allylic rearrangement of the linalyl carbocation in geranyl and neryl carbocation and than the cyclization in terpinyl carbocation. Solvolyse of linalyl acetate is 120 times faster than solvolyse of geranyl acetate and of neryl acetate .…”

Section: Chemical Reactions Happening During Growing Ripening Storamentioning

confidence: 99%

Bitter orange peel essential oil: A review of the different factors and chemical reactions influencing its composition

Gaff

Decloux

Giampaoli

2020

Flavour & Fragrance J

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This review summarizes the findings and discusses the results on the different factors that can influence the bitter orange peel oil composition. Small changes in composition can result in noticeable modifications of the odour profile of the essential oil. The analysis method appears to have a crucial effect on the number of compounds identified in the essential oil. Growing location, cultivar, ripening stage, storage conditions and extraction methods are reported to impact the bitter orange essential oil. Bitter orange peel oil should be stored at −21°C to prevent changes in the composition and formation of artefacts when storing for a period of several months. The influence of cultivars should not be neglected, since a few cultivars differ a lot from the main cluster of Citrus aurantium L. The geranyl pyrophosphate forms most of the terpenes present in the bitter orange, especially limonene which is the majority compound, by the action of the terpene synthases during growing of the fruit. The extraction method can also be responsible for some differences in the composition due to the absence of water‐soluble compounds in cold‐pressed oils and to acid‐catalysed reactions in hydrodistilled oils such as the decomposition of the linalyl acetate forming many different terpene derivatives.

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Section: Chemical Reactions Happening During Growing Ripening Storamentioning

confidence: 99%

Bitter orange peel essential oil: A review of the different factors and chemical reactions influencing its composition

Gaff

Decloux

Giampaoli

2020

Flavour & Fragrance J

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“…2) (19,20) that debinds from the enzyme (in an as-yet-undefined fashion) to complete the reaction cycle. This transformation constitutes one of the least complicated of all terpenoid cyclization reactions (21), and it is one of very few that has ample precedent in biomimetic solvolysis studies (22)(23)(24). The widespread occurrence of limonene also implies an equally broad distribution of LSs in the plant kingdom.…”

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confidence: 99%

“…This proposal implies that the helical, cyclization-competent conformation of LPP, predicted from biochemical studies (1,18,25), is achieved directly only when LPP is bound from solution when it can adopt this thermodynamically stable form. This conformational difference in binding, coupled with the inherently faster solvolytic rate of the tertiary allylic system (22)(23)(24), readily explains the faster rate of enzymatic cyclization of LPP than GPP by LS (15) and other monoterpene synthases (1,18 (51). The two fluoroanalogs were characterized by using their 3 H, 19 F, and 31 P NMR spectra.…”

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confidence: 99%

Structure of limonene synthase, a simple model for terpenoid cyclase catalysis

Hyatt¹,

Youn

Zhao

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

210

249

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The crystal structure of (4S)-limonene synthase from Mentha spicata, a metal ion-dependent monoterpene cyclase that catalyzes the coupled isomerization and cyclization of geranyl diphosphate, is reported at 2.7-Å resolution in two forms liganded to the substrate and intermediate analogs, 2-fluorogeranyl diphosphate and 2-fluorolinalyl diphosphate, respectively. The implications of these findings are described for domain interactions in the homodimer and for changes in diphosphate-metal ion coordination and substrate binding conformation in the course of the multistep reaction.crystal structure ͉ geranyl diphosphate ͉ linalyl diphosphate ͉ monoterpene cyclase ͉ monoterpene synthase

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“…Principal conversion of geraniol ( 4b ) to geranyl chloride ( 2c , Table 1, entry 1) likely occurs through a direct displacement30 whereas formation of terpenyl chloride ( 2e ) requires a change in olefin stereochemistry. Isomerization of geraniol ( 4b ) to linaloyl chloride ( 2b ) is precedented43 and would facilitate an ionic or NbCl 5 -promoted cyclization to terpenyl chloride ( 2e ) 44…”

Section: Resultsmentioning

confidence: 99%

Allylic and Allenic Halide Synthesis via NbCl₅- and NbBr₅-Mediated Alkoxide Rearrangements

2009

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Addition of NbCl 5 , or NbBr 5 , to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metallahalo-[3,3] rearrangement although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure E-allylic or allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones.

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Rearrangement of linalool, geraniol, nerol and their derivatives

Cited by 35 publications

References 0 publications

Bitter orange peel essential oil: A review of the different factors and chemical reactions influencing its composition

Bitter orange peel essential oil: A review of the different factors and chemical reactions influencing its composition

Structure of limonene synthase, a simple model for terpenoid cyclase catalysis

Allylic and Allenic Halide Synthesis via NbCl₅- and NbBr₅-Mediated Alkoxide Rearrangements

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Rearrangement of linalool, geraniol, nerol and their derivatives

Cited by 35 publications

References 0 publications

Bitter orange peel essential oil: A review of the different factors and chemical reactions influencing its composition

Bitter orange peel essential oil: A review of the different factors and chemical reactions influencing its composition

Structure of limonene synthase, a simple model for terpenoid cyclase catalysis

Allylic and Allenic Halide Synthesis via NbCl5- and NbBr5-Mediated Alkoxide Rearrangements

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Allylic and Allenic Halide Synthesis via NbCl₅- and NbBr₅-Mediated Alkoxide Rearrangements