- Synthesis of carboxymethyl GLA-60 ether derivatives containing an olefin in their chains and their LPS-antagonistic activities
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Anomeric carboxymethyl GLA-60 olefine derivatives having ether chains instead of ester chains in their side chains were synthesized and their biological activities toward both human U937 cells and mouse PEC-macrophage cells were measured. The species-specific behavior of these compounds in humans (LPS-antagonistic) and mice (very weak LPS-antagonistic, but almost inactive) found this time was different from that in humans (LPS-antagonistic) and mice (endotoxic) found in the biosynthetic precursor of lipid A, such as lipid IVa. However, this fact also shows, interestingly enough, that a difference exists in the molecular recognition between human and mouse LPS receptors.
- Nakamura, Tsuyoshi,Watanabe, Yukiko,Shiozaki, Masao,Kanai, Saori,Kurakata, Shin-ichi
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p. 1011 - 1022
(2007/10/03)
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- Sex pheromone of female vine bud moth, Theresimima ampellophaga comprises (2s)-butyl (7z)-tetradecenoate
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The sex pheromone of the vine bud moth, Theresimima ampellophaga, released at the 3rd-5th abdominal tergites, was identified by coupled GC-EAG, GC-MS, and synthesis as (2S)-butyl (7Z)-tetradecenoate. For the first time, full stereochemistry is unambiguously defined for the sex pheromone of a member of the Zygaenidae. The synthetic compound caught significant numbers of males in field-trapping experiments.
- Subchev,Harizanov,Francke,Franke,Plass,Reckziegel,Schroeder,Pickett,Wadhams,Woodcock
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p. 1141 - 1151
(2007/10/03)
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- Vinylic Organoboranes. 4. A General, One-Pot Synthesis of 6- and 7-Alkyn-1-ols via Boracyclanes. Influence of Steric Effects in the Iodination of Lithium Alkynyl "Ate" Complexes of Dialkylborinates
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The iodination of the "ate" complexes derived from various B-alkoxyborinane derivatives and 1-alkynyllithium has been investigated.The results indicate the ate complex from B-methoxyborinane is converted into desired 6-alkyn-1-ol in a yield of only 22percent, with much larger amounts, 65percent, of the undesired 1-iodo-1-alkyne.Increases in the steric bulk of the alkoxy group on boron increase the yield of the required 6-alkyn-1-ol with the best results realized with B-(triphenylmethoxy)borinane.Treatment of B-(triphenylmethoxy)borinane with 1-alkynyllithium affords the corresponding "ate" complex.Subsequent iodination induces the migration of one end of the cycloalkyl chain from boron to the adjacent carbon, resulting in the formation of the one-carbon homologated borepane moiety.This then undergoes a rapid deiodoboronation to afford the corresponding (6-alkyn-1-yl)boronate ester.Oxidation of these esters produces the desired 6-alkyn-1-ols in excellent yields (85percent).An attempt to extend this reaction to di-n-alkylborinates to prepare the corresponding unsymmetrical alkynes did not achieve satisfactory results.Alternatively, the iodination of the "ate" complex from B-methylborinane and 1-alkynyllithium, followed by oxidation, provides the required 6-alkyn-1-ols in high yields.This procedure has been successfully extended to the seven-membered borepane moiety to provide the corresponding 7-alkyn-1-ols.Extension of this reaction to the di-n-alkylmethylboranes provides the corresponding unsymmetrical alkynes in good yields.Thus, these procedures constitute a simple, general and one-pot synthesis of the desired alkyn-1-ols, valuable synthons in organic synthesis.Insect pheromones, (Z)-7-tetradecenaland (Z)-7-hexadecenal, were readily prepared in excellent yields by utilizing this convenient procedure.
- Brown, Herbert C.,Basavaiah, D.,Bhat, N. G.
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p. 4518 - 4521
(2007/10/02)
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- Sec-butyl (Z)-7-tetradecenoate and its use as a sex attractant for the grapeleaf skeletonizer
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A pheromonal compound produced by the western grapeleaf skeletonizer has been identified as sec-butyl (Z)-7-tetradecenoate. The synthetically-prepared compound demonstrates activity toward both the western grapeleaf skeletonizer, Harrisina brillians Barnes and McDunnough and the grapeleaf skeletonizer, Harrisina americana (Guerin). By attracting adult moths to field traps, this compound offers a useful tool in monitoring and control of this pest.
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- INSECT SEX PHEROMONES. STEREOSELECTIVE SYNTHESIS OF SEVERAL (Z)- AND (E)-ALKEN-1-OLS, THEIR ACETATES, AND OF (9Z,12E)-9,12-TETRADECADIEN-1-YL ACETATE
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Several female sex pheromone components produced by moths belonging to the order of Lepidoptera, and potential attractants of Dacus oleae (Diptera:Tripetidae) have been synthesized in high chemical and stereoisomeric purity by improved acetylenic routes involving alkylation of lithium 1-alkyn-1-ides in HMPT, followed by (Z) and (E) highly stereoselective reduction of the derived internal alkynes.Particular care has been paid to optimize the parameters of the reactions used and to evaluate the chemical and isomeric purity of the reaction products.The compounds synthesized include (Z)- and (E)-5-nonen-1-ol, (Z)- and (E)-7-dodecen-1-yl acetate, (Z)- and (E)-7-teradecen-1-yl acetate, (Z)- and (E)-7-nonen-1-ol, (Z)- and (E)-9-tetradecen-1-yl acetate, (Z)- and (E)-10-tetradecen-1-yl acetate, (Z)- and (E)-11-tetradecen-1-yl acetate.Pure (Z)-6-nonen-1-ol, which is an attractant of olive fruit fly, D. oleae, and very probably, a constituent of the sex pheromone of females of this insect, has been prepared by a rather efficient copper-catalyzed reaction between (Z)-3-hexen-1-ylmagnesium bromide and oxetane. (9Z,12E)-9,12-Tetradecadien-1-yl acetate, which is the pheromone of Anagasta kuenniella, Ephestia elutella, Cadra figulella, Spodoptera exigua, S. litura, and a component of the sex pheromones of several other Lepidoptera, has been conveniently prepared by using the copper-catalyzed coupling reaction between (E)-1-chloro-2-butene and 10-tetrahydropyranyloxy-1-decenylmagnesium bromide, followed by acetylation and Z-stereoselective reduction of the derived 1,4-enyne.All syntheses have been conducted on a scale to yield less than 50 mmol of the pure sex pheromone components, but seem adaptable for much larger quantities.
- Rossi, Renzo,Carpita, Adriano,Gaudenzi, Loretta,Quirici, Maria Grazia
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p. 237 - 246
(2007/10/02)
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