1986
DOI: 10.1021/jo00358a028
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Rearrangement of linalool, geraniol, nerol and their derivatives

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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%
“…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%
“…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.…”
mentioning
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.…”
mentioning
confidence: 99%
“…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%