83602-78-2Relevant academic research and scientific papers
Pheromone synthesis. Part 257: Synthesis of methyl (2E,4Z,7Z)-2,4,7-decatrienoate and methyl (E)-2,4,5-tetradecatrienoate, the pheromone components of the male dried bean beetle, Acanthoscelides obtectus (Say)
Mori, Kenji
, p. 5589 - 5596 (2015/08/03)
Tandem Dess-Martin oxidation/Wittig reaction of (2Z,5Z)-2,5-octadien-1-ol yielded methyl (2E,4Z,7Z)-2,4,7-decatrienoate, a newly discovered pheromone component of the male dried bean beetle, while that of (±)-2,3-dodecadien-1-ol gave (±)-methyl (E)-2,4,5-tetradecatrienoate, the racemate of the known and major pheromone component. Methyl (2E,4E,7Z)-2,4,7-decatrienoate was also synthesized, which is the methyl ester of an acid metabolite of a green alga. Reduction of 2,5-octadiyn-1-ol with Zn-Cu/EtOH cleanly gave (2Z,5Z)-2,5-octadien-1-ol.
Enantioselective synthesis of allenylenol silyl ethers via chiral lithium amide mediated reduction of ynenoyl silanes and their Diels-Alder reactions
Sasaki, Michiko,Kondo, Yasuhiro,Moto-Ishi, Ta-Ichi,Kawahata, Masatoshi,Yamaguchi, Kentaro,Takeda, Kei
, p. 1280 - 1283 (2015/03/14)
An enantioselective Meerwein-Ponndorf-Verley-type reduction of ynenoylsilanes by a chiral lithium amide followed by a Brook rearrangement and anti-mode protonation across conjugated 1,3-enynes provides allene derivatives bearing a 2-siloxyvinyl moiety in high enantioselectivity. The E/Z geometry of enol silyl ethers is controlled by the geometry of the starting enyne moiety. Thus, (E)- and (Z)-enol silyl ethers are obtained from (Z)- and (E)-ynenoylsilans, respectively. The 2-siloxyvinylallene products can participate in Diels-Alder reactions with reactive dienophiles such as PTAD, which can be achieved in a one-pot operation from ynenoylsilanes.
Pheromone synthesis. Part 249: Syntheses of methyl (R,E)-2,4,5- tetradecatrienoate and methyl (2E,4Z)-2,4-decadienoate, the pheromone components of the male dried bean beetle, Acanthoscelides obtectus (Say)
Mori, Kenji
experimental part, p. 1936 - 1946 (2012/04/10)
The enantiomers of methyl (E)-2,4,5-tetradecatrienoate (1), a component of the male pheromone of Acanthoscelides obtectus, were synthesized from the enantiomers of 1-undecyn-3-ol (6), which were obtained via asymmetric acetylation of (±)-1-trimethylsilyl-1-undecyn-3-ol (4) with vinyl acetate as catalyzed by lipase PS (Amano). The ortho ester Claisen rearrangement of 6 with triethyl orthoacetate was the key-step to generate the chiral allenic system. A new synthesis of (±)-1 was also executed starting from (±)-6. Three different syntheses of methyl (2E,4Z)-2,4-decadienoate (2), another component of the male pheromone of A. obtectus, were achieved by means of either palladium-catalyzed Heck reaction or a Claisen and an Al 2O3 catalyzed thermal rearrangements.
An 1,2-Elimination Approach to the Enantioselective Synthesis of 1,3-Disubstituted Linear Allenes
Zhang, Yan,Hao, Hong-Dong,Wu, Yikang
supporting information; experimental part, p. 905 - 908 (2010/08/05)
The construction of 1,3-disubstituted allene skeleton, which is present in many natural allenes, via an i-PrMgBr-mediated elimination of optically active 3-acetoxy-2-iodo-prop-1-ene derviatives is exemplified through the enantioselective total synthesis o
A new route to methyl (R,E)-(-)-tetradeca-2,4,5-trienoate (pheromone of Acanthoscelides obtectus) utilizing a palladium-catalyzed asymmetric allene formation reaction
Ogasawara, Masamichi,Nagano, Takashi,Hayashi, Tamio
, p. 5764 - 5767 (2007/10/03)
A formal total synthesis of the sex attractant of male dried bean beetle, methyl (R,E)-(-)-tetradeca-2,4,5-trienoate, was achieved by a new efficient route utilizing the Pd-catalyzed asymmetric allene synthesis reaction. It was found that the atropisomeric biaryl bisphosphine (R)-segphos showed better enantioselectivity than (R)-binap in the Pd-catalyzed reaction for preparing alkyl-substituted axially chiral allenes.
A new method for synthesis of allenes, including an optically active form, from aldehydes and alkenyl aryl sulfoxides by sulfoxide-metal exchange as the key reaction and an application to a total synthesis of male bean weevil sex attractant
Satoh, Tsuyoshi,Hanaki, Noriko,Kuramochi, Yuko,Inoue, Yujiro,Hosoya, Kayo,Sakai, Ken
, p. 2533 - 2549 (2007/10/03)
The sulfoxide-metal exchange reaction of β-acetoxy sulfoxides or β-mesyloxy sulfoxides, which were derived from alkenyl aryl sulfoxides and aldehydes in two steps, with a Grignard reagent or alkyllithium at low temperature gave allenes in good yields. Optically active allenes were synthesized starting from optically active 2-substituted ethenyl p-tolyl sulfoxides. A synthesis of (-)-methyl (E)-2,4,5-tetradecatrienoate, a male bean weevil sex attractant, was realized by this method.
Amplification of chirality by transition metal coordination: Synthesis of chiral allenes and allene manganese complexes of high enantiomeric purity. Synthesis of methyl (R,E)-(-)-(2,4,5-tetradecatrienoate (pheromone of Acanthoscelides obtectus (say))
Franck-Neumann, Michel,Martina, Daniel,Neff, Denis
, p. 697 - 708 (2007/10/03)
The enhancement of the asymmetry of choreal oiliness by coordination with a transition metal can be turned to account for (easy) resolution of the complexes and therefore the oiliness themselves. This is illustrated here on allene aldehyde complexes of (η
LOW-MOLECULAR-MASS BIOREGULATORS. II. SYNTHESIS OF METHYL (+/-)-TETRADECA-2E,4,5-TRIENOATE-THE SEX PHEROMONE OF Acanthoscelides obtectus
Melikyan, G. G.,Mkrtchyan, V. M.,Atanesyan, K. A.,Azaryan, G. Kh.,Badanyan, Sh. O.
, p. 78 - 82 (2007/10/02)
A preparative method has been developed for obtaining methyl (+/-)-tetradeca-2E,4,5-trienoate - the racemate of the sex pheromone of the dried-bean beetle.Using methyl 4-chlorotetradec-5-ynoate as an example, a detailed study has been made of the dependence of the regiochemistry of reduction on the activity of a zinc-copper couple, the methods of its activation, and the acidity of the proton donor.
STEREOSELECTIVE PREPARATION OF CONJUGATED DIENOATES AND DIENAMIDES. NEW SYNTHESIS OF PELLITORINE AND PIPERCIDE
Bloch, Robert,Hassan-Gonzales, Dominique
, p. 4975 - 4982 (2007/10/02)
(E) and (E,E)-conjugated dienoates and dienamides of high stereoisomeric purities are prepared via thermal SO2 extrusion from cis-2,5-disubstituted-2,5-dihydrothiofene-1,1-dioxides generated by a retro Diels-Alder reaction.Applications of this method to the syntheses of two insecticidal natural dienamides : pellitorine and pipercide and of methyl tetradeca-2E,4,5-trienoate, an insect sex pheromone, are described.
