50767-78-7Relevant academic research and scientific papers
Efficient preparation of terminal conjugated dienes by coupling of dienol phosphates with grignard reagents under iron catalysis
Cahiez, Gerard,Habiak, Vanessa,Gager, Olivier
supporting information; experimental part, p. 2389 - 2392 (2009/05/27)
(Chemical Equation Presented) An efficient new route to prepare stereoselectively terminal conjugated dienes by coupling Grignard reagents and dienol phosphates in the presence of Fe(acac)3 is described. The synthetic utility of this new iron-catalyzed procedure is illustrated by the synthesis of the pheromone of Diparopsis castanea according to a very expeditious strategy.
Stereospecific synthesis of (E)-9-11-dodecadien-1-yl acetate, a sex pheromone of red bollworm (Diparopsis catenea)
Singh, Vasundhara,Vig, Rakesh,Trehan, I R,Kad, G L
, p. 50 - 52 (2007/10/02)
Ireland-Claisen rearrangement of 3-acetoxy-11-(tetrahydropyranyloxy)undec-1-ene (3) gives 13-(tetrahydropyranyloxy)-4(E)-tridecen-1-oic acid (4) stereospecifically.Oxidative decarboxylation of 4 followed by acetylation furnishes (E)-9,11-dodecadien-1-yl acetate (6) in good yield.
A novel palladium-catalyzed deoxygenation of enediols to 1,3-dienes
Trost,Tometzki
, p. 1235 - 1245 (2007/10/02)
Hydroxylative Knoevenagel condensation of aldehydes followed by reduction provides a simple entry to 1,4-enediols. Subjecting the dicarbonate to a palladium(0) catalyst in the presence of triisopropyl phosphite achieves a mild vinylogous deoxygenation to (E)-1,3-dienes. Stereocontrolled synthesis of the sex pheromone of the red bollworm moth, (E)-9,11-dodecadienyl acetate, and a formal synthesis of the cotton boll weevil antifeedant, α-eleostearic acid, demonstrate the utility of this new methodology.
A new synthesis of 9,11-dodecadienyl-1-acetate
Muralikrishna, Chivukala,Dasaradhi, Lakkaraju,Rao, Samala Jagadishwar,Bhalerao, U. T.
, p. 579 - 580 (2007/10/02)
Allylation of 9-bromononaldehyde (3) affords the key intermediate hydroxyalkene (4) which on acetylation followed by dehydration gives the title pheromone (1) in quantitative yield.
"Ene"-Type Reaction of the Pummerer Rearrangement Product Derived from 4-Chlorophenyl Methyl Sulphoxide: Synthesis of Some Insect Sex Pheromones
Ishibashi, Hiroyuki,Komatsu, Hajime,Ikeda, Masazumi
, p. 2548 - 2561 (2007/10/02)
The Pummerer rearrengement product (8) derived from 4-chlorophenyl methyl sulphoxide (7) and trifluoroacetic anhydride undergoes an ene type reaction with terminal olefins to give the products (9).Oxidation of (9) followed by thermolysis of the resultant sulphoxides provides a general synthesis of the terminal conjugated dienes (10).Using this method, dodeca-9,11-dienyl acetate (16), the sex pheromone of the red bollworm moth, has been prepared.Transformations of the ene products (9) to some other insect sex pheromones such as bombykol (20) and tetradec-11-enyl acetate (24) are also described.
METHOXY(PHENYLTHIO)METHANE AS AN AMBI-EQUVIVALENT OF A METHOXY- OR PHENYLTHIOMETHYLENE 1,1-DIPOLE
Sato, Tsuneo,Okura, Shuji,Otera, Junzo,Nozaki, Hitosi
, p. 6299 - 6302 (2007/10/02)
Methoxy(phenylthio)methane undergoes electrophilic alkylation followed by nucleophilic allylation or propargylation which is dramatically changed depending on the Lewis acid employed providing a methoxy- or phenylthiomethylene 1,1-dipole synthon.
Stereoselective Synthesis of (E)-, (E,Z)-, and (E,E)-Conjugated Dienes via Alkylation of 3-Sulfolenes as the Key Step
Yamada, Sachiko,Ohsawa, Hideto,Suzuki, Takayoshi,Takayama, Hiroaki
, p. 4934 - 4940 (2007/10/02)
A new stereoselective method is presented for synthesizing (E)-, (E,Z)-, and (E,E)-conjugated dienes via alkylation of 3-sulfolenes as the key step.Direct alkylation of 3-sulfolene at the 2-position proceeds with good yields when labile sulfolene α-carbanion is generated in the presence of alkyl iodides in THF-HMPA solution at -78 deg C.Alkylation of 2-alkyl-3-sulfolenes gives trans-2,5-dialkyl-3-sulfolenes with 100percent regioselectivity and more than 90percent stereoselectivity.Desulfonylation of trans-3,5-disubstituted 3-sulfolenes is examined in detail, and the conditions to give stereoselectively the corresponding (E,Z)-and (E,E)-conjugated dienes are found.Applying the method, three insect pheromones, (E)-9,11-dodecadien-1-yl acetate, a sex pheromone of the red bollworm moth, (E,E)-8,10-dodecadien-1-ol, a sex pheromone of the codling moth, and (E,E)-11,13-hexadecadienal, a sex pheromone of the cabbage webworm, are easily synthesized by starting with 3-sulfolene with nearly 100percent stereoselectivity.Synthesis of cis-3,4,5-trisubstituted cyclohexenes using 2-substituted 3-sulfolenes as the diene synthons is also described.
ALKYLATION OF DIENE ALLYLIC TERTIARY AMINES WITH GRIGNARD REAGENTS. IN SITU ACTIVATION WITH ALKYL CHLOROFORMATES.
Langlois, Yves,Van Bac, Nguyen,Fall, Yagamare
, p. 1009 - 1012 (2007/10/02)
Diene allylic tertiary amines were substituted with Grignard reagents in the presence of lithium tetrachlorocuprate and alkyl chloroformates.According to the experimental condition employed, this reaction afforded exclusively γ-alkylation products.
Mass Spectra of Dodecadienic Compounds with a Conjugated Double Bond, Lepidopterous Sex Pheromones
Ando, Tetsu,Katagiri, Yoshio,Uchiyama, Masaaki
, p. 413 - 422 (2007/10/02)
All geometrical isomers of 5,7-, 6,8-, 7,9-, 8,10- and 9,11-dodecadien-1-ols, and their acetates and aldehyde derivatives were analyzed by electron impact mass spectrometry.The abundance of molecular ion (M(1+)) was observed in every spectrum, and the relative intensity of M(1+) tended to be strong if the compound possessed an (E)-double bond(s).In addition to M(1+), (1+) (alcohols) and (1+) (acetates), every dienic compound showed typical series of CnH(2n-2)(1+)CnH(2n-5)(1+) with abundance maxima around C4, C5, C6 or C7.Each double bond positional isomer characteristically yielded different ion peaks in the series, which were useful for its distinction from other isomers.These results indicate that the chemical structure of a natural pheromone of Lepidoptera is easily deduced successfully by GC-MS analysis if it is a conjugated dienic pheromone.
