Preparation of Ketones from the Reaction of Organolithium Reagents with Carboxylic Acids

Jorgenson, Margaret J.

doi:10.1002/0471264180.or018.01

Cited by 9 publications

(9 citation statements)

References 204 publications

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“…2-Acetoxyheptadecane was prepared from 2-heptadecanone synthesized previously at NRI by addition of methyl lithium to hexadecanoic acid in ether (Jorgenson 1970 All other positional isomers of acetoxyheptadecane were synthesized by reduction and acetylation of the corresponding heptadecanones, which were available commercially or were synthesized by addition of an organolithium to a carboxylic acid (Jorgenson 1970). (2S,12Z)-2-Acetoxy-12-heptadecene, the pheromone of the pistachio twig borer, Kermania pistaciella (Gries et al 2006), was kindly provided by Prof. Gerhard Gries.…”

Section: Methodsmentioning

confidence: 99%

Identification of Female-produced Sex Pheromone of the Honey Locust Gall Midge, Dasineura gleditchiae

et al. 2009

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The honey locust gall midge, Dasineura gleditchiae Osten Sacken 1866 (Diptera: Cecidomyiidae) is the main pest of ornamental varieties of the honey locust tree, Gleditsia triacanthos L., in North America, and is now becoming a pest of concern in Europe. Female midges were observed to emerge in the early morning with their ovipositor extended until they mated. Volatiles were collected from virgin females in a closed-loop stripping apparatus and analyzed by gas chromatography (GC) coupled to electroantennographic (EAG) recording from the antenna of a male midge. A single EAG response was observed, which was assumed to be to the major component of the female sex pheromone. This was identified as (Z)-2-acetoxy-8-heptadecene by comparison of its mass spectrum and GC retention times on different columns with those of synthetic standards and by micro-analytical reactions. This compound was synthesized, and the individual enantiomers were produced by kinetic resolution with lipase from Candida antarctica. Analysis of the naturally-produced compound on a cyclodextrin GC column indicated it was the (R)-enantiomer. In EAG dose-response measurements, the (R)-enantiomer alone or in the racemic mixture evoked significant responses from the antennae of male D. gleditchiae, whereas the (S)-enantiomer did not. In field trapping tests, the (R)-enantiomer attracted male D. gleditchiae. The racemic compound was equally attractive, but the (S)-enantiomer was not attractive. Both the pure (R)-enantiomer or racemic (Z)-2-acetoxy-8-heptadecene, applied to red rubber septa in a dose range of 3-30 microg, constitute a strongly attractive bait in sticky traps for monitoring the flight of D. gleditchiae.

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Section: Methodsmentioning

confidence: 99%

Identification of Female-produced Sex Pheromone of the Honey Locust Gall Midge, Dasineura gleditchiae

et al. 2009

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“…Oxalyl chloride, as a carbonylated reagent, had been reported to undergo substitution reactions with two equivalents of mono-functionalized organometallic compounds, such as Grignard reagents, and organolithium and organocopper compounds, to form 1,2-disubstituted 1,2-diones [38][39][40][41][42][43]. However, when organodimetallic reagents of these organometallic compounds were used, the reaction frequently led to the formation of complexes, or an inseparable mixture because of over-addition, polymerization or decomposition.…”

Section: Reactions Of Zirconacycles 21 11-cycloaddition Of Oxalyl Dmentioning

confidence: 99%

Zirconacycle-mediated synthesis of carbocycles

Chen

2010

Chin. Sci. Bull.

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Direct transformation of five-membered zirconacycles to carbocyclic compounds is of great synthetic interest. The reaction of zirconacycles with electrophiles containing at least two reactive functional groups or an oxidant affords various carbocycles through cross coupling, addition, and/or oxidative coupling reactions. In this paper, we present our recent results on the zirconacycle-mediated formation of carbocycles, including: (1) 1,1-cycloaddition of oxalyl dichloride with zirconacycles; (2) benzoquinone-promoted coupling of zirconacyclopentadienes in the presence of CuCl; (3) cycloaddition of zirconacyclopentadienes to quinones; (4) cycloaddition of zirconacyclopentadiene with 2-bromoacrylate, 2-bromoacrylaldehyde and 3-bromofuran-2,5-dione in the presence of CuCl; (5) one-pot coupling of two alkynes and an alkene to form cyclohexene derivatives via zirconacyclopentadienes; and (6) dianionic cycloaddition of decatetraenes with esters or acyl chlorides to form nine-membered carbocycles.

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“…2-Butyroxyheptadecane was prepared from 2-heptadecanone synthesized previously at NRI by addition of methyl lithium to hexadecanoic acid in ether (Jorgenson 1970 (2S,12Z)-2-Acetoxy-12-heptadecene, the pheromone of the pistachio twig borer, Kermania pistaciella (Gries et al 2006), was kindly provided by Professor Gerhard Gries. A sample was hydrolyzed with potassium carbonate in methanol to give (2S,12Z)-8-heptadecen-2-ol, and this was reacted with butyryl chloride and pyridine in dichloromethane to give a sample of (2S,12Z)-2-butyroxy-12-heptadecene.…”

Section: Micro-analytical Reactionsmentioning

confidence: 99%

(2S,8Z)-2-Butyroxy-8-heptadecene: Major Component of the Sex Pheromone of Chrysanthemum Gall Midge, Rhopalomyia longicauda

et al. 2009

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The sex pheromone of the chrysanthemum gall midge, Rhopalomyia longicauda (Diptera: Cecidomyiidae), the most important insect pest in commercial plantations of chrysanthemum, Dendranthema morifolium (Ramat.) Tzvel., in China, was identified, synthesized, and field-tested. Volatile chemicals from virgin females and males were collected on Porapak in China and sent to the United Kingdom for analysis. Coupled gas chromatographic-electroantennographic detection (GC-EAG) analysis of volatile collections from females revealed two compounds that elicited responses from antennae of males. These compounds were not present in collections from males. The major EAG-active compound was identified as 2-butyroxy-8-heptadecene by gas chromatographic (GC) retention indices, mass spectra, in both electron impact and chemical ionization modes, hydrogenation, epoxidation, and derivatization with dimethyldisulfide. The lesser EAG-active compound was identified as the corresponding alcohol. The ratio of butyrate to alcohol in the collections was 1:0.26. Racemic (Z)-8-heptadecen-2-ol and the corresponding butyrate ester were synthesized from (Z)-7-hexadecenyl acetate, and the synthetic compounds found to have identical GC retention indices and mass spectra to those of the natural, female-specific components. Analysis of the volatile collections on an enantioselective cyclodextrin GC column showed the natural pheromone contained (2S,8Z)-2-butyroxy-8-heptadecene. Field tests showed that rubber septa containing racemic (Z)-2-butyroxy-8-heptadecene were attractive to R. longicauda males. The (naturally occurring) S-enantiomer was equally as attractive as the racemate, while the R-enantiomer was not attractive to males, and did not inhibit the activity of the S-enantiomer. The attractiveness of the butyrate was significantly reduced by the presence of even small amounts of the corresponding alcohol.

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Preparation of Ketones from the Reaction of Organolithium Reagents with Carboxylic Acids

Cited by 9 publications

References 204 publications

Identification of Female-produced Sex Pheromone of the Honey Locust Gall Midge, Dasineura gleditchiae

Identification of Female-produced Sex Pheromone of the Honey Locust Gall Midge, Dasineura gleditchiae

Zirconacycle-mediated synthesis of carbocycles

(2S,8Z)-2-Butyroxy-8-heptadecene: Major Component of the Sex Pheromone of Chrysanthemum Gall Midge, Rhopalomyia longicauda

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