1965
DOI: 10.1002/jlac.19656900107
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Organische Fluorverbindungen, IX1). Fluorisoprenole

Abstract: Lithiumalanat reduziert cr.P-ungesattigte y-Fluorcarbonsaureester (z. B. 1) bei -78" zu y-Fluorisoprenolen. Bei hoherer Temperatur tritt als nachster Reaktionsschritt die reduktive Eliminierung des Fluors ein. Daneben findet, weitgehend Temperatur-unabhangig, iiber einen Additions-Eliminierungsmechanismus eine intramolekulare nucleophile Substitution des Fluors statt. Fortschreitende Reduktion fiihrt zu Hydroxymethyl-cyclopropanen (z. B. 9). 8-Fluor-geraniol (39) laRt sich nicht auf klassischem Wege darstellen… Show more

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Cited by 12 publications
(5 citation statements)
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“…16 Compound 8 was initially subjected to a Horner-Emmons reaction with triethyl phosphonoacetate to generate bromoester 9 with good stereoselectivity (E : Z = 11 : 1). 17 Reduction of the ester with DIBAL-H in THF at 278 uC followed by protection of the resulting alcohol with a THP group gave 10b in near quantitative yield. This compound was converted to the phosphonium bromide salt 11 and then treated with 1,3difluoroacetone in a Wittig reaction to give 12a in 87% yield.…”
mentioning
confidence: 99%
“…16 Compound 8 was initially subjected to a Horner-Emmons reaction with triethyl phosphonoacetate to generate bromoester 9 with good stereoselectivity (E : Z = 11 : 1). 17 Reduction of the ester with DIBAL-H in THF at 278 uC followed by protection of the resulting alcohol with a THP group gave 10b in near quantitative yield. This compound was converted to the phosphonium bromide salt 11 and then treated with 1,3difluoroacetone in a Wittig reaction to give 12a in 87% yield.…”
mentioning
confidence: 99%
“…Analogue 9, 4-fluorofarnesyl pyrophosphate, was prepared by phosphorylation of (2£,6£)-4-fluorofarnesol exactly as described for the other pyrophosphates. The fluorinated alcohol was obtained by LiAlH4 reduction of ethyl 4-fluorofarnesoate (Machleidt and Grell, 1965; Ortiz de Montellano and Vinson, 1977). Since the alcohol precursors of all the pyrophosphate analogues except 5 were obtained by metal hydride reduction of the corresponding ethyl esters, the C-l tritium-labeled compounds were made by reduction of the esters with [3H]LiAlH4.…”
Section: Methodsmentioning
confidence: 99%
“…In the hydrolysis of -yfluorobutyronitrile and 0 -fluorovaleronitrile with concentrated hydrochloric acid, o-chlorobutyric and -ychlorovaleric acids were obtained instead of the expected An interesting displacement of fluorine involving an intramolecular 5HZ" reaction is shown below. 13 Ring-closure with elimination of ftuorine occurred also in ketones containing enolizable carbonyl and capable of forming five-membered rings." Displacement of fluorine is especially easy when a primary or secondary amino group is within the reach.…”
Section: Entry 7)mentioning
confidence: 99%