Copper-catalyzed cross-coupling of (Z)-allyl phenyl ethers with Grignard compounds in the synthesis of insect pheromones

Petrushkina, E. A.; Калинин, В. Н.

doi:10.1134/s1070363208100125

Cited by 5 publications

(3 citation statements)

References 12 publications

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“…2-Propyn-1-ol (3) with dimethyl sulfate was transformed in methyl propargyl ether (4) which under action of potassium tert-butoxyd gave methoxyallene (5).…”

Section: Resultsmentioning

confidence: 99%

“…The reaction mixture was refluxed 4 h and after that was distilled in vacuum of 2-3 mm Hg. The collection flask was cooled externally up to -70 0 C. It was obtained 67g (957 mmoles) of methoxyallene (5). Yield: 87%.…”

Section: Methoxyallene (5)mentioning

confidence: 99%

“…The synthesis of (Z)-8-dodecene-1-yl acetate and (E)-8dodecene-1-yl acetate are well known in the literature [2][3][4][5]. The paper [6] decribes synthesis of the (11Z, 13Z)hexadecadiene-1-yl acetate and (13Z)-hexadecen-11-ynyl acetate, using cross-coupling reactions for the stereospecific introduction of double bonds.…”

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confidence: 99%

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A Practical Synthesis of (Z)- and (E)-8-Dodecene-1-yl Acetate, Components of Lepidoptera Insect Sex Pheromones

Ciotlaus¹,

Gansca²,

Andreica³

et al. 2017

Rev. Chim.

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New and practical synthesis of (Z)-8-dodecene-1-yl acetate and (E)-8-dodecene-1-yl acetate were developed. The synthesis were based on a C3+C6=C9 and C9+C3=C12 coupling scheme, the starting material being 2-propyn-1-ol and 1,6-hexandiol. The routes involve, as the key step, the use of the same mercury derivative of the terminal-alkyne w-functionalised as intermediate. The first coupling reaction took place between methoxyallene and Grignard reagent of 1-tert-butoxy-6-bromo-hexan obtaining 1-tert-butoxy-non-8-yne, which is transformed in di[1-tert-butoxy-non-8-yne]mercury, the common intermediate in the synthesis of the two pheromones. In order to obtain (Z)-8-dodecene-1-yl acetate and (E)-8-dodecene-1-yl acetate, the mercury derivative was directly lithiated and then alkylated with 1-bromo-propan obtaining 1-tert-butoxy-dodec-8-yne. After acetylation of 1-tert-butoxy-dodec-8-yne and stereoselective reduction in the presence of NiP-2 catalyst gave (Z)-8-dodecene-1-yl acetate with 85 % isomeric purity. After reduction with lithium aluminium hydride of 1-tert-butoxy-dodec-8-yne and acetylation was obtained (E)-8-dodecene-1-yl acetate with 90% isomeric purity.

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“…2-Propyn-1-ol (3) with dimethyl sulfate was transformed in methyl propargyl ether (4) which under action of potassium tert-butoxyd gave methoxyallene (5).…”

Section: Resultsmentioning

confidence: 99%

Section: Methoxyallene (5)mentioning

confidence: 99%

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A Practical Synthesis of (Z)- and (E)-8-Dodecene-1-yl Acetate, Components of Lepidoptera Insect Sex Pheromones

Ciotlaus¹,

Gansca²,

Andreica³

et al. 2017

Rev. Chim.

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Concise Syntheses of Insect Pheromones Using Z‐Selective Cross Metathesis

et al. 2012

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The shortest synthetic routes to nine cis-pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported. These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z-olefins. Important insight into the mechanism of Z-selective metathesis was uncovered during experimentation and subsequently explored. KeywordsZ-olefin; insect pheromone; olefin metathesis; seed oil derivatives; unconjugated diene The use of insect sex pheromones to limit specifically targeted pest populations has gained increasing popularity as a viable, safe, and environmentally-friendly alternative to insecticides. While broad spectrum insecticides are toxic compounds that have been shown to adversely affect human health, [1] extensive studies have revealed that insect pheromones are nontoxic and safe for human consumption at the levels used in pest control practices. [2] Female sex pheromones are mainly employed in pest control in a process termed mating

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