- Method for synthesizing sex pheromone of anarsia lineatella
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The invention belongs to the technical field of green pesticide synthesis, and discloses a novel method for synthesizing sex pheromone of anarsia lineatella. The method comprises the following steps:with 5-hexyn-1-ol as a raw material, subjecting 5-hexyn-1-ol and1-bromobutane to a nucleophilic substitution reaction in the presence of n-butyllithium and HMPA to generate 5-decyn-1-ol, then performing reduction via lithium aluminum hydride to obtain (E)-5-decen-1-ol, and finally performing an acetylation reaction to obtain (E)-5-decen-1-ol acetate. According to the invention, a triple bond of alkyne is reduced into an E-type double bond by lithium aluminum hydride, so the method has the advantages of simple synthetic route, mild reaction conditions, good environmental compatibility and the like.
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Paragraph 0011; 0022-0024
(2020/05/30)
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- Enantioselective Aza-Heck Cyclizations of N-(Tosyloxy)carbamates: Synthesis of Pyrrolidines and Piperidines
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Pd(0)-systems modified with SPINOL-derived phosphoramidate ligands promote highly enantioselective aza-Heck cyclizations of alkenyl N-(tosyloxy)carbamates. The method provides versatile access to challenging N-heterocycles and represents the broadest scope enantioselective aza-Heck protocol developed to date.
- Ma, Xiaofeng,Hazelden, Ian R.,Langer, Thomas,Munday, Rachel H.,Bower, John F.
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supporting information
p. 3356 - 3360
(2019/03/07)
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- Synthesizing method for 5E-decene-1-alcohol and acetic acid 5E-decenoate
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The invention provides a synthesizing method for 5E-decene-1-alcohol and acetic acid 5E-decenoate. With acrylaldehyde and acetylene being raw materials, a coupling reaction is carried out under the existence of a palladium catalyst to obtain 5-bromo-4E-pentenal, 5-bromo-4E-pentenal and methoxy methyl-triphenyl phosphonium chloride are subjected to a Wittig reaction to obtain 1E,5E-1-bromo-6-methoxy hexadiene, then 1E,5E-1-bromo-6-methoxy hexadiene and butyl magnesium bromide are subjected to a Kumada coupling reaction to obtain 1E,5E-1-methoxy decadiene, 5E-decenal is obtained through hydrolysis, then 5E-decene-1-alcohol is obtained through reducing, and finally the acetic acid 5E-decenyl acetate is obtained after esterification. The raw materials used for synthesis are low in price and easy to obtain, the synthesizing route is simple, reaction conditions are mild, operation is convenient and safe, industrialized production is easy, the yield is high, and the synthesizing method has important meaning for prevention and treatment of anarsia lineatella.
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- SYNTHESIS OF OLEFINIC ALCOHOLS VIA ENZYMATIC TERMINAL HYDROXYLATION
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In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.
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- Selective deoxygenation of allylic alcohol: Stereocontrolled synthesis of lavandulol
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Selective deoxygenation of allylic alcohol can be successfully carried out by the formation of alkoxyalkyl ether (EE or MOM), followed by Pd(dppe)Cl 2-catalyzed reduction with LiBHEt3. (+)-S-Lavandulol has been efficiently synthesized by the application of this protocol to the diol derived from the Pb(OAc)4-promoted oxidative ring-opening of (-)-R-carvone. This deoxygenation method is general and selective for allylic alcohols.
- Kim, Hee Jin,Su, Liang,Jung, Heejung,Koo, Sangho
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p. 2682 - 2685
(2011/06/26)
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- A selective Ru-catalyzed semireduction of alkynes to Z olefins under transfer-hydrogenation conditions
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By using a readily available, air- and moisture-stable dihydrido-Ru complex, a variety of Z olefins are accessible under transfer-hydrogenation conditions with formic acid as the hydrogen source in excellent yields and Z/E selectivities. A discerning transformation: Z-Configured C=C bonds are stereoselectively formed from alkynes in the presence of a Ru catalyst with formic acid as the sole H2 source at room temperature (see scheme). A variety of functional groups are compatible with this novel procedure. Operational simplicity and the lack of overreduction products are characteristics for this unprecedented process.
- Belger, Christian,Neisius, N. Matthias,Plietker, Bernd
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supporting information; experimental part
p. 12214 - 12220
(2011/03/17)
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- Biologically active compounds by catalytic olefin metathesis
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Biologically active compounds such as pheromones and precursors thereof are produced by catalyzed cross metathesis of dissimilar terminal olefins or of a cyclodiene and a terminal olefin.
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- Preparation of alkenols
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A process for preparing alkenols of the formula I where R1 is hydrogen or a hydrocarbon radical, and n is an integer from 3 to 15, a) by reacting a phosphonium salt of the formula IIa where X is chlorine, bromine or iodine, with an aldehyde of the formula IIIa or its hemiacetal of the formula IIIb STR1 or b) by reacting a phosphonium salt of the formula IIb with a aldehyde of the formula IV in a solvent in the presence of a base, wherein the base is the alkali metal salt of an alcohol and the solvent is an alcohol.
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- Metal/Ammonia Reduction of Ethers of 3-Decyn-1-ol: Effects of Structure and Conditions on Cleavage and Rearrangement
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Reduction of the THP, ethyl, tert-butyl and tert-butyldimethylsilyl (TBDMS) ethers of 3-decyn-1-ol with sodium in ammonia/THF results in extensive hydrogenolysis of the carbon-oxygen bond and concomitant bond migration, producing a mixture of 2- and 3-decenes and a very low yield of the desired (E)-homoallylic ether.Reduction in the presence of 2-methyl-2-propanol led to excellent yields of the desired (E)-3-decenol ethers.The 4- and 5-decyn-1-ol ethers were reduced normally to the (E)-decen-1-ol ethers except in the case of the TBDMS ethers which were cleaved to the (E)-alcohols under some of the reaction conditions.
- Doolittle, Robert E.,Patrick, Delrea G.,Heath, Robert H.
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p. 5063 - 5066
(2007/10/02)
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- Reactions of α-epoxysilanes with organocopper reagents. A stereoselective route to alkenes
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Reactions of α-epoxysilanes with cuprate reagents can be controlled to give β-silyl alcohols as major products. An oxidation, Grignard addition, and elimination sequence then provides alkenes with up to 98% de.
- Chauret, Denise C.,Chong, J. Michael
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p. 3695 - 3698
(2007/10/02)
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- Triply Convergent, Stereospecific Alkene Formation via Peterson Olefination
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α-Iodo silanes 8 were prepared from α-hydroxy silanes and after halogen/metal exchange and treatment with copper(I)bromide-dimethyl sulfide were coupled with acid chlorides to yield α-silyl ketones 2.Cram controlled addition with a variety of nucleophiles followed by treatment with acid or base led to either the (E)- or (Z)-alkene in good overall yields from the iodide (47-67percent) and with excellent stereoselectivities (>95/95/5 isomeric purity.
- Barrett, Anthony G. M.,Flygare, John A.
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p. 638 - 642
(2007/10/02)
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- Cyclic ethers as educts for the synthesis of lepidoptra pheromones
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ω-Iodo(trialkylsiloxy)alkanes 2 prepared by ring opening of cyclic ethers with iodotrimethylsilane, are useful starting materials for the synthesis of pheromone components. Reaction with triphenylphosphine to give the corresponding Wittig reagent and subsequent coupling with lithium (Z)-dihex-1-enylcuprate gives (Z)-alken-1-ols 5 and 7, after deprotection, in good yields. The direct coupling of 2 with alkynes failed because of competition reactions, however, the more stable ω-iodo-1-(tert-butyldimethylsiloxy)alkanes were able to undergo C,C-coupling with alkynes. The thus formed 1-(tert-butyldimethylsiloxy)-5-decyne (13c) was hydrogenated and deprotected to give (E)-5-decen-1-ol (15c).
- Poleschner,Heydenreich,Martin
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p. 1231 - 1235
(2007/10/02)
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- SYNTHESIS OF PHEROMONES, IV. CHEMISTRY OF THE WITTIG REACTION, I. EFFECTS OF REACTION CONDITIONS ON THE STEREOSELECTIVITY AND YIELD OF THE WITTIG REACTION
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The reactions of nonstabilized triphenylphosphorus ylides with aldehydes have been studied in detail.The stereochemistry and yields of the alkene products are highly dependent upon base used for the generation of the ylide, the solvent and reaction temperature.The synthesis of sex pheromone components by Wittig reaction are also described.
- Vinczer, Peter,Juvancz, Zoltan,Novak, Lajos,Szantay, Csaba
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p. 797 - 820
(2007/10/02)
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- Applications of the Stereochemically-Controlled Horner-Wittig Reaction: Synthesis of Feniculin, (E)-Non-6-en-1-ol, a Pheromone of the Mediterranean Fruit Fly, (E)- and (Z)-Dec-5-en-1-ol, Tri-substituted Alkenes, and (Z)-α-Bisabolene
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Stereoselective reduction of the appropriate α-diphenylphosphinoyl ketone or addition of the lithium derivative of an alkyl diphenylphospine oxide to an aldehyde or a ketone gives Horner-Wittig intermediates and hence the title compounds.
- Buss, Antony D.,Greeves, Nicholas,Mason, Ralph,Warren, Stuart
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p. 2569 - 2578
(2007/10/02)
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- STEREOCHEMICALLY CONTROLLED SYNTHESIS OF UNSATURATED ACIDS VIA DIPHENYLPHOSPHINOYL(Ph2PO)-KETOACIDS
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Acylation of phosphine oxide anions with derivatives of cyclic anhydrides or oxidative cleavage of cyclic allyl phosphine oxides gives Ph2PO-ketoacids: reduction, separation of diastereoisomers, and completion of the Horner-Wittig reaction gives single isomers (E or Z) of unsaturated acids.
- Levin, Daniel,Warren, Stuart
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p. 505 - 508
(2007/10/02)
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- INSECT PHEROMONES AND THEIR ANALOGS. XII. SYNTHESIS OF THE ISOMERIC DEC-5-ENYL ACETATES - THE SEX PHEROMONES OF Anarsia lineatella AND Agrotis segetum
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A new route for the synthesis of dec-5E- and -5Z-enyl acetates - the sex pheromones of the peach-tree borer and of the turnip moth - is proposed which is based on the two-stage hydroxyethylation of hex-1-yne using 2-chloroethyl vinyl ethers and ethylene oxide.
- Odinokov, V. N.,Balezina, G. G.,Ishmuratov, G. Yu.,Vakhitov, R. Sh.,Tolstikov, G. A.
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p. 369 - 371
(2007/10/02)
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- SYNTHESIS OF SINGLE ISOMERS (E OR Z) OF UNSATURATED ALCOHOLS BY THE HORNER-WITTIG REACTION
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Single isomers (E or Z) of homoallylic and higher alcohols can be synthesised from ω-hydroxyalkyldiphenylphosphine oxides and aldehydes, or from alkyldiphenylphosphine oxides and lactones
- Buss, Antony D,Greeves, Nicholas,Levin, Daniel,Wallace, Paul,Warren, Stuart
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p. 357 - 360
(2007/10/02)
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- A Convenient Synthesis of (E)-9-Tetradecen-1-yl Acetate, a Sex Pheromone of Gelechiid Moth and (E)-5-Decenol, a Sex Pheromone of Peach Twig Borer
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n-Butyllithium reacts with dihydropyran to give (E)-4-nonenyl alcohol (IV).The alcohol (IV) is converted into the corresponding bromide (V).The Grignard reagent of the bromide (V) on coupling with the bromide (VI) in the presence of Li2CuCl4, followed by hydrolysis yields the alcohol (III).This on acetylation gives the pheromone (I).The formylation of the Grignard reagent prepared from V gives the pheromone (II).
- Chattopadhyay, A.,Mamdapur, V. R.,Chadha, M. S.
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p. 1221 - 1223
(2007/10/02)
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- Synthesis of (E)-5-Decen-1-ol, a Sex Pheromone, Isolated from Peach Twig Borer Moth Anarsia lineatella
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Protection of one of the alcoholic function of pentane-1,5-diol with dihydropyran gives the THP ether (II) which on oxidation with Corey's reagent furnishes the aldehyde (III). 5-Tetrahydropyranyloxypentan-1-al (III) on treatment with vinylmagnesium bromide in dry THF provides the alcohol (IV) which on mercuric acetate catalysed transetherification with ethyl vinyl ether yields 7-tetrahydropyranyloxy-3-vinyloxyhept-1-ene (V).Claisen migration of the vinyl ether (V) under N2 atmosphere provides the aldehyde (VI) in quantitative yield.LAH reduction of VI, followed by reaction of the resulting alcohol (VII) with mesyl chloride affords 1-mesyloxy-9-tetrahydropyranyloxy-non-4(E)-ene (VIII).Reaction of lithium dimethylcuprate on mesylate (VIII) in dry ether at -10 deg C under N2 atmosphere provides 10-tetrahydropyranyloxydec-5(E)-ene (IX) which on treatment with conc.HCl in methanol gives (E)-5-decen-1-ol (I).
- Vig, O. P.,Sharma, M. L.,Gakhar, Madhu,Malik, Neera
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p. 755 - 757
(2007/10/02)
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- Carbon-Carbon Bond Formation by the Use of Chloroiodomethane as a C1 Unit. II. The Preparation and Synthetic Application of 1-Chloro-3-iodoheptane
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Terminal alkenes, R-CH=CH2 (R=Et, n-Pr, n-Bu, N-Hex), were readily transformed into 1-chloro-3-iodoalkanes by the AIBN-induced free radical addition of chloroiodomethane.Thus, 1-chloro-3-iodoheptane was obtained from 1-hexene in an 88percent yield; this in turn was allowed to react with dialkyl malonates in the presence of alkoxides in alcohols to give dialkyl 2-butylcyclobutane-1,1-dicarboxylates and dialkyl (E)-3-octene-1,1-dicarboxylates (7), either of which could be obtained preferentially by the choice of the experimental parameters.The olefinic product, 7, was further utilized for the synthesis of (E)-5-decenyl acetate and/or 1,4-nonanolide.
- Miyano, Sotaro,Hokari, Hiroshi,Umeda, Yoshiharu,Hashimoto, Harukichi
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p. 770 - 774
(2007/10/02)
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