- Efficient preparation of terminal conjugated dienes by coupling of dienol phosphates with grignard reagents under iron catalysis
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(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.
- Cahiez, Gerard,Habiak, Vanessa,Gager, Olivier
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supporting information; experimental part
p. 2389 - 2392
(2009/05/27)
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- Stereospecific synthesis of (E)-9-11-dodecadien-1-yl acetate, a sex pheromone of red bollworm (Diparopsis catenea)
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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.
- Singh, Vasundhara,Vig, Rakesh,Trehan, I R,Kad, G L
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- A novel palladium-catalyzed deoxygenation of enediols to 1,3-dienes
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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.
- Trost,Tometzki
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p. 1235 - 1245
(2007/10/02)
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- A new synthesis of 9,11-dodecadienyl-1-acetate
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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.
- Muralikrishna, Chivukala,Dasaradhi, Lakkaraju,Rao, Samala Jagadishwar,Bhalerao, U. T.
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p. 579 - 580
(2007/10/02)
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- METHOXY(PHENYLTHIO)METHANE AS AN AMBI-EQUVIVALENT OF A METHOXY- OR PHENYLTHIOMETHYLENE 1,1-DIPOLE
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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.
- Sato, Tsuneo,Okura, Shuji,Otera, Junzo,Nozaki, Hitosi
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p. 6299 - 6302
(2007/10/02)
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- "Ene"-Type Reaction of the Pummerer Rearrangement Product Derived from 4-Chlorophenyl Methyl Sulphoxide: Synthesis of Some Insect Sex Pheromones
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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.
- Ishibashi, Hiroyuki,Komatsu, Hajime,Ikeda, Masazumi
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p. 2548 - 2561
(2007/10/02)
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- Stereoselective Synthesis of (E)-, (E,Z)-, and (E,E)-Conjugated Dienes via Alkylation of 3-Sulfolenes as the Key Step
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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.
- Yamada, Sachiko,Ohsawa, Hideto,Suzuki, Takayoshi,Takayama, Hiroaki
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p. 4934 - 4940
(2007/10/02)
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- ALKYLATION OF DIENE ALLYLIC TERTIARY AMINES WITH GRIGNARD REAGENTS. IN SITU ACTIVATION WITH ALKYL CHLOROFORMATES.
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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.
- Langlois, Yves,Van Bac, Nguyen,Fall, Yagamare
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p. 1009 - 1012
(2007/10/02)
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- Mass Spectra of Dodecadienic Compounds with a Conjugated Double Bond, Lepidopterous Sex Pheromones
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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.
- Ando, Tetsu,Katagiri, Yoshio,Uchiyama, Masaaki
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p. 413 - 422
(2007/10/02)
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- (E)- AND (Z)-1-BENZENESULFONYL-4-TRIMETHYLSILYL-2-BUTENES AS (E)-1-(1,3-BUTADIENYL) SYNTHONS
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(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes (E/Z=9), prepared from 4-trimethylsilyl-1-buten-3-ol, n-butyllithium and benzenesulfenyl chloride and oxidation of the intermediate (E)- and (Z)-1-benzenesulfinyl-4-trimethylsilyl-2-butenes with hydrogen peroxide, react with n-butyllithium and then primary halides to give 4-benzenesulfonyl-1-trimethylsilyl-2-alkenes which are rapidly 1,4-debenzenesulfonyltrimethylsilated to (E)-1,3-alkadienes by tetra-n-butylammonium fluoride at 0 deg C.
- Hsiao, C-N.,Shechter, H.
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p. 1219 - 1222
(2007/10/02)
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- Regiochemical Convergence in the Reaction of Heterosubstituted Allylic Carbanions via Allylic Aluminum and Boron "Ate" Complexes
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The regiochemistry in reactions of heterosubstituted allylic carbanions (1) is highly controlled via allylic aluminum or boron "ate" complexes which direct both carbonyl compounds and reactive halides to the α-position with high regioselectivity.For example, carbonyl compounds react with the oxygen- (3), sulfur- (12), selenium- (20), and silicon- (25) substituted allylic carbanions at the α-position via the ate complexes.Although the reactions of the ate complexes (2) with aldehydes generally produce a mixture of erythro and threo isomers, the aluminum ate comlex of 3b gives the erythro isomer (5) with very high stereoselectivity.This procedure is applied to the stereoselective synthesis of exo-brevicomin (9).With allylic halides, the oxygen- (3a) and sulfur- (12) substituted allylic carbanions again react at the α-position via the ate complexes.However, the coupling mode is entirely different; the α-α' coupling product (10) is obtained from 3a, while the α-γ' coupling product (15) is produced from 12.
- Yamamoto, Yoshinori,Yatagai, Hidetaka,Saito, Yoshikazu,Maruyama, Kazuhiro
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p. 1096 - 1104
(2007/10/02)
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- Une synthese hautement stereoselective de dienes conjugues (E)
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A general method for the preparation of (E) terminal conjugated dienes was developed by the flash thermolysis of 2-substituted 2,5-dihydrothiophene-1,1-dioxides generated by a retro Diels-Alder reaction.This process allows the obtention of conjugated dienes, bearing or not a functionality (alcohols, esters), with an excellent stereoisomeric purity (in general higher than 98percent).An application to the synthesis of (E)-9,11-dodecadien-1-yl acetate, the major component of the sex pheromone of Diparopsis castanea, shows the generality and the efficacy of this method.
- Bloch, R.,Abecassis, J.,Hassan, D.
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p. 2019 - 2024
(2007/10/02)
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- A Highly Stereo- and Regioselective Synthesis of (E)-1,3-dienes and (E,E)-1,3,5-trienes
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(E)-1,3-dodecadien-1-yl acetate, an insect sex pheromone of the red bollworm moth and (E,E)-1,3,5-undecatriene, a component of Dictyopteries and Galbanum were synthesized in a highly stereo- and regioselective manner from allyl and pentadienyl dithiocarbamates, respectively.
- Hayashi, Toshio,Yanagida, Masako,Matsuda, Yuko,Oishi, Takeshi
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p. 2665 - 2668
(2007/10/02)
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- Stereoselective Syntheses of E- and Z-9,11-Dodecadien-1-yl Acetates: The Major Sex Pheromones of the Red Bollworm Moth
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The sex pheromones 1 and 2 of the red bollworm moth were synthesized in a highly stereoselective manner.The key step of their syntheses was the olefination reaction of E- and Z-allyl phenyl sulfones 8 and 12, affording the corresponding dienes 9 and 15, respectively.Keywords - E-9,11-dodecadien-1-yl acetate; Z-9,11-dodecadien-1-yl acetate; sex pheromone; red bollworm moth; allyl sulfone; tri-n-butylstannylmethyl iodide
- Ochiai, Masahito,Ukita, Tatsuzo,Fujita, Eiichi
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p. 1641 - 1645
(2007/10/02)
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- STEREOSELECTIVE SYNTHESIS OF (E)-, (E,Z)- AND (E,E)-CONJUGATED DIENES VIA ALKYLATION OF 3-SULFOLENES AS KEY STEP
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Stereoselective method for synthesizing (E)-, (E,Z)- and (E,E)-conjugated dienes via alkylation of 3-sulfolenes as key step is developed.Sex pheromones with (E)- and (E,E)-conjugated diene structures are synthesized with exclusively high stereoselectivity by applying the method.
- Yamada, Sachiko,Ohsawa, Hideto,Suzuki, Takayoshi,Takayama, Hiroaki
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p. 1003 - 1006
(2007/10/02)
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- A HIGHLY STEREOSELECTIVE SYNTHESIS OF (E)-1- SUBSTITUTED-1,3-DIENES.
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(E)-1-substituted-1,3-dienes are obtained with high selectivity by the thermal extrusion of SO2 from 2-substituted-2,5-dihidrothiophene-1,1-dioxides generated by a retro Diels-Alder reaction.An application to the synthesis of (E)-9,11-dodecadien-1-yl acetate, a sex pheromone of the red-bollworm moth is described.
- Bloch, R.,Abecassis, J.
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p. 3277 - 3280
(2007/10/02)
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- Simple, Stereospecific Syntheses of Some Insect Pheromones using the -Fe(CO)3 Protecting Group
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(Diene)Fe(CO)3 complexes have been used for totally stereospecific syntheses of insect pheromones having (E)- and (E,E)-1,3-diene skeletons.
- Knox, Graham R.,Thom, Ian G.
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p. 373 - 374
(2007/10/02)
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- A STEREOCONTROLLED SYNTHESIS OF Z AND E TERMINAL DIENES FROM PINACOL E-1-TRIMETHYLSILYL-1-PROPENE-3-BORONATE
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Pinacol E-1-trimethylsilyl-1-propene-3-boronate reacts with aldehydes to form (+)-(R*, S*)-3-trimethylsilyl-4-hydroxy-1-alkenes, which can be deoxysilylated stereoselectively to either 98percent Z or 99percent E 1,3-dienes, including the separate components of the red bollworm moth pheromone.
- Tsai, David Jieh Shyh,Matteson, Donald S.
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p. 2751 - 2752
(2007/10/02)
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- A STEREOSPECIFIC SYNTHESIS OF 12-ACETOXY-1,3-DODECADIENE, THE SEX PHEROMONE OF DIPAROPSIS CASTANEA (HAMPSON)
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A stereospecific synthesis of 12-acetoxy-1,3(E)-dodecadiene, 1, the pheromone of the Diparopsis castanea Hampson, via the alkylation of the anion of 2-(2-propyne-1-oxy)tetrahydropyran, 5a, and successive reduction with LiAlH4, is described.
- Cardillo, Giuliana,Orena, Mario,Porzi, Gianni,Sandri, Sergio
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p. 523 - 526
(2007/10/02)
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- Synthesis of 9(E)-Dodecenyl Acetate & 9(E),11-Dodecadienyl Acetate, Female Sex Pheromones of red Bollworm Moth, Diparopsis castanea Hmps.
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Undec-10-en-1-ol (III) on the reaction with dihydropyran in the presence of catalytic amount of conc.HCl at 0 deg C provides the ether (IV) which on epoxidation with m-chloroperbenzoic acid yields the epoxide (V) in very high yields.Cleavage of V with lithium diisopropylamide under N2 atmosphere gives the 11-tetrahydropyranyloxyundec-2(E)-en-1-ol (VI) which on oxidation with pyridinium chlorochromate in dry CH2Cl2 furnishes 11-tetrahydropyranyloxyundec-2(E)-en-1-al (VII).Aldehyde (VII) on Wittig reaction using methylenetriphenylphosphorane in DMSO under N2 atmosphere affords conjugated diene (VIII) which on treatment with methanolic solution of PTS gives 9(E),11-dodecadien-1-ol (IX).Action of isopropenyl acetate on IX in the presence of PTS yields 9(E),11-dodecadienyl acetate (I).Conversion of the intermediate alcohol (VI) into the corresponding mesylate (X) with mesyl chloride/ triethylamine in dry CH2Cl2 at 0 deg and subsequent treatment of X with lithium dimethyl cuprate under N2 atmosphere results in the formation of 12-tetrahydropyranyloxyundec-3(E)-ene (XI).Removal of the protective pyranyl group in XI with PTS in methanol gives 9(E)-dodecenol (XII) which on treatment with acetic anhydride/ dry pyridine provides 9(E)-dodecenyl acetate.
- Vig, O. P.,Sharma, M. L.,Verma, N. K.,Malik, Neera
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p. 692 - 694
(2007/10/02)
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