- A NOVEL SYNTHESIS OF LINEAR POLYENES VIA CONJUGATE ADDITION OF CUPRATES TO α,β-γ,δ-DIUNSATURATED SULFONES FOLLOWED BY SO2 EXTRUSION
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The two 1,3-butadienyl 2-propenyl sulfones 5 and 6, 1,3,5-heptatriene synthons, have been transformed into the tri- and tetraenes 1 - 4 by alkylcuprate addition and Ramberg-Baecklund SO2 extrusion.The reaction stereochemistry is discussed.
- Naef, Ferdinand,Decorzant, Rene,Escher, Sina D.
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Read Online
- Photoinduced Palladium-Catalyzed Carbofunctionalization of Conjugated Dienes Proceeding via Radical-Polar Crossover Scenario: 1,2-Aminoalkylation and beyond
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A photoinduced palladium-catalyzed 1,2-carbofunctionalization of conjugated dienes has been developed. This mild modular approach, which does not require employment of exogeneous photosensitizers and external oxidants, allows for efficient and highly regio- and stereoselective synthesis of a broad range of allylic amines from readily available 1,3-dienes, alkyl iodides, and amines. Employment of O- and C-nucleophiles toward oxyalkylation and dialkylation products was also demonstrated. A putative π-allyl palladium radical-polar crossover path is proposed as a key event in this three-component coupling process. The utility of this protocol is highlighted by its application for derivatization of several amine-containing drugs.
- Gevorgyan, Vladimir,Kurandina, Daria,Shing Cheung, Kelvin Pak,Yata, Tetsuji
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supporting information
p. 9932 - 9937
(2020/06/27)
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- METHOD FOR PRODUCING COMPOUND HAVING CONJUGATED DIENE STRUCTURE
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PROBLEM TO BE SOLVED: To provide a method capable of industrially producing a conjugated diene or a conjugated triene in a short process from a raw material which is easy to obtain and handle. SOLUTION: A conjugated diene is produced from a 3-alkenal via reactions of the following first step, second step, and third step in this order: the first step of reacting a Grignard reagent with the 3-alkenal to obtain a homoallylic alcohol; a second step of reacting an esterification reagent or a halogenation reagent with the homoallylic alcohol to obtain a sulfonic ester or a halogenated product; and a third step of having a base act on the sulfinic acid ester or the halogenated product to cause an elimination reaction. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0043
(2019/08/12)
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- An approach to the regioselective diamination of conjugated di- and trienes
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It's do or diaminate: The selective diamination of 1,3-butadienes in the presence of hypervalent iodine reagents has been developed. This oxidation process proceeds with complete selectivity in favor of diamination. Depending on the substrate, it proceeds either with 1,2- or 1,4-regioselectivity (see scheme). Copyright
- Lishchynskyi, Anton,Muniz, Kilian
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supporting information; experimental part
p. 2212 - 2216
(2012/03/27)
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- Synthesis of naturally occurring diene and trienes by Te/Li exchange on (1Z,3Z)-butyltelluro-4-methoxy-1,3-butadiene
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(1Z,3Z)-Butyltelluro-4-methoxy-1,3-butadiene 2 was obtained by the hydrotelluration of (Z)-1-methoxy-but-1-en-3-ynes 1. The butadienyllithium 3 obtained by the Te/Li exchange reaction in the (1Z,3Z)-1-butyltelluro-4-methoxy-1,3-butadiene 2 reacted with aldehydes to form the corresponding alcohols 4a-d with total retention of configuration. The alcohols formed undergo hydrolysis, resulting in the α,β,γ,δ-unsaturated aldehydes of (E,E) configuration, which are precursors of trienes obtained from natural sources. The products of this reaction were employed in the synthesis of methyl-(2E,4E)-decadienoate 7, which is a component of the flavor principles of ripe Bartlett pears. Performing the Wittig reaction of the methyl triphenylphosphorane with the deca-(2E,4E)-dienal 5a, we were able to synthesize the undeca-(1,3E,5E)-triene 6a. This compound is a sex-pheromone component of the marine brown algae Fucus serratus, Dictyopteris plagiograma, and Dictyopteris australis. Performing the Wittig reaction of methyl triphenylphosphorane with the octa-(2E,4E)-dienal 5c, the nona-(1,3E,5E)-triene 6b was synthesized. The compound obtained is a sex-pheromone component of the marine brown alga Sargassum horneri. The octa-(1,3E,5E)-triene 6c was easily obtained from hepta-(2E,4E)-dienal 5d by the Wittig reaction with methyl triphenylphophorane. This compound is a sex-pheromone component of the marine brown alga Fucus serratus.
- Dabdoub, Miguel J.,Dabdoub, Vania B.,Baroni, Adriano C.M.,Hurtado, Gabriela R.,Barbosa, Sandro L.
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experimental part
p. 1666 - 1670
(2010/05/19)
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- A new synthetic route to 1,3,5-undecatrienes and fucoserratene
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A new procedure for preparing natural alkatrienes, fucoserratene and 1,3,5-undecatrienes, was developed. The key step of both syntheses is stereoselective formation of double bonds by the Wittig reaction starting from (E)-4,4-dimethoxy-2-butenal.
- Garibyan,Ovanesyan,Makaryan,Chobanyan
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p. 455 - 458
(2008/09/20)
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- The preparation and electrocyclic ring-opening of cyclobutenes: Stereocontrolled approaches to substituted conjugated dienes and trienes
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Thermal electrocyclic ring-opening of 4-alkyl-2-cyclobutene-1-carbaldehydes occurs at low temperature to give (2Z,4E)-alkadienals exclusively, and the process is exploited in transforming cis-3-cyclobutene-1,2-dimethanol 1 into a variety of naturally occurring 1,3,5-alkatrienes and 2,4-decadienoates. Desymmetrisation of 1 with Pseudomonas fluorescens lipase gives access to both enantiomers of 3-oxabicyclo[3.2.0]hept-6-en-2-one 4, for use in stereocontrolled routes to 6-oxygenated (2Z,4E)-alkadienals.
- Binns, Falmai,Hayes, Roy,Hodgetts, Kevin J.,Saengchantara, Suthiweth T.,Wallace, Timothy W.,Wallis, Christopher J.
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p. 3631 - 3658
(2007/10/03)
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- An efficient synthesis of 1,3(E),5(Z), 1,3(E),5(E)and 1,3(Z),5(Z)-trienes: Application to the synthesis of galbanolenes and (9Z,11E)-9,11,13-tetradecatrien-1-yl acetate
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The (Pd-Cu)-catalyzed reactions of trimethylsilyl acetylene with (E) or (Z)-chloroenynes, or 1-chloro-(1E,3E)-dienes, followed by desilylation and zinc-reduction of the triple bonds led respectively to (3E,5Z), (3Z,5Z) and (3E,5E)-trienes. Application to the syntheses of galbanolenes and (9Z,11E)-9,11,13-tetradecatrien-1-yl acetate has been realized.
- Alami, Mouad,Gueugnot, Sylvie,Domingues, Elisa,Linstrumelle, Gerard
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p. 1209 - 1220
(2007/10/02)
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- Stereoselective synthesis of polyenes via Heck coupling of vinylboronate esters
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E- and Z-1-alkenyl iodides react with vinylboronate pinacol ester 1 under palladium(0) catalysed, Heck conditions to provide polyenylboronates in moderate yields after purification. The addition of either silver(I) or thallium(I) salts to the reaction mixture is essential. Alkenyl bromides are unreactive under identical reaction conditions.
- Stewart, Sarah K.
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p. 3925 - 3928
(2007/10/02)
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- Process for the preparation of polyunsaturated olefins
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A process for the preparation of a polyunsaturated olefinic compound, i.e. undeca-1,3,5-triene, in its (3E,5Z) isomeric form, consisting of four consecutive steps starting from deca-1,4-diyne, is disclosed. Said process has the advantage of making it possible to obtain the desired isomer in its essentially pure form.
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- Use of cis-3-cyclobutene-1,2-dimethanol in stereoselective routes to some naturally occurring conjugated dienes and trienes
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Thermal electronic ring-opening of 4-alkyl-2-cyclobutene-1-carbaldehydes occurs at low temperature to give (2Z,4E)-alka-2,4-dienals exclusively, and this process is exploited en route to various isomeric naturally occurring 1,3,5-alkatrienes and 2,4-decadienoates from a single precursor, cis-3-cyclobutene-1,2-dimethanol 4.
- Hodgetts, Kevin J.,Saengchantara, Suthiweth T.,Wallis, Christopher J.,Wallace, Timothy W.
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p. 6321 - 6324
(2007/10/02)
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- New Triene Synthesis from Sorbic Acid: Two-Step Synthesis of cis- and trans-Galbanolenes
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The lithium dianion of sorbic acid reacts with hexanal at the C(2)-position to afford separable anti- and syn-hydroxy carboxylic acids 3 and 4 (87percent; 3/4=59:41 or 79percent; 3/4=16:84), whose stereospecific anti-decarboxylative elimination respectively affords (3E,5Z)- and (3E,5E)-1,3,5-undecatriene (1) and (2) (cis- and trans-galbanolenes (1) and (2) (69percent).An alternative route to 1 involves conversion of 3,4 to cis-lactone 7 (45percent after chromatography) followed by thermal syn-decarboxylation (81percent).The described procedure is both new and of general applicability, as illustrated by the synthesis of trienes with different substitution pattern.Key Words: Sorbic acid; aldol reaction; triene synthesis; olefination; decarboxylative elimination.
- Fehr, Charles,Galindo, Jose,Chappuis, Simone
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p. 2465 - 2468
(2007/10/02)
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- Two new stereoselective syntheses of (3E,5Z)-1,3,5-undecatriene
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Two new and short syntheses of (3E,5Z)-1,3,5-undecatriene 1 are presented. Both approaches are based on the coupling between a C7 and a C4 synthon and afford 1 in 92-96% stereoisomeric purity.
- Gaudin, Jean-Marc,Morel, Cedric
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p. 5749 - 5752
(2007/10/02)
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- Novel, Readily occurring, and Stereoselective Synthesis of Conjugated Trienes using 2-Trialkylstannyl-2,5-dihydrothiophene S,S-Dioxide
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Conjugated trienes have been synthesized readily and stereoselectively by the coupling reaction of 2-tri-n-butylstannyl-2,5-dihydrothiophene S,S-dioxide with vinyl iodides in he presence of tetrakis(triphenylphosphine)palladium(0), followed by desulphonylation.
- Takayama, Hiroaki,Suzuki, Takayoshi
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p. 1044 - 1045
(2007/10/02)
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- SYNTHESE DES UNDECATRIENES-1,3-5 NATURELS
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The reaction of organometallics with (E)-dichloroethylene in the presence of palladium and nickel catalysts, leads to an efficient stereoselective synthesis of 1, 3E, 5E-undecatrien and its isomer 1, 3E, 5Z.
- Ratovelomanana, Victorin,Linstrumelle, Gerard
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p. 174 - 176
(2007/10/02)
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- New process for the preparation of 1,3,5-undecatrienes
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Process for the preparation of 1,3,5-undecatrienes, characterized in that an organometallic 1-heptenyl compound is reacted with a (E)-1,3-butadiene derivative. Manufacture of 1,3,5-undecatrienes that can be used in the perfumes and flavorings industry.
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- HIGHLY STEREO- AND REGIOSELECTIVE PALLADIUM-CATALIZED SYNTHESES OF (3E,5Z)-(3E,5E)-,AND (3Z,5E)-1,3,5-UNDECATRIENE
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(3E,5Z)-1,3,5-Undecatriene (3) having 98.2percent stereoisomeric purity has been prepared by a new and expeditious route involving two selective Pd-catalyzed carbon-carbon bond forming reactions.The key step of this synthesis is a highly diastereoselective Pd-catalyzed cross-coupling reaction between 1-heptynylzinc chloride (11a) and a molar excess of (E)/(Z)-1,2-dibromoethylene (12). Another highly diastereoselective Pd-catalyzed reaction, which involves a cross-coupling between trimethylsilylethynylzinc chloride (15) and molar excesses of stereoisomeric mixtures of 1-bromo-1-alkenes (16), has been used to prepare (E)-1-trimethylsilyl-3-nonen-1-yne (10a), a key intermediate for the synthesis of (3E,5E)- and (3Z,5E)-undecatriene, (4) and (5).Compounds 3 and 4, isolated from the essential oil of Ferula galbaniflua, also occur together with compound 5 in the male attracting oils of seaweeds.These substances have odors highly appreciated in perfumery.
- Andreini, Bianca Patrizia,Benetti, Massimiliano,Carpita, Adriano,Rossi, Renzo
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p. 4591 - 4600
(2007/10/02)
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- Method for the preparation of sulfones and compounds containing carbon chains having conjugated unsaturation and the compounds resulting from such method
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A method for the preparation of a first sulfone compound of the formula: STR1 wherein Ra is STR2 where Rb is Br and Rc is H except that Rb and Rc together may be an electron pair when R6 is a radical of the formula: STR3 wherein X1 is independently chlorine, bromine or iodine and R1 and R2 are independently at each occurrence hydrogen or, substituted or unsubstituted, phenyl or alkyl where the substituents are halogen or alkoxy or additional --SO2 Br groups; provided that, each carbon atom of R1 or R2 which contains --SO2 Br also contains an X1 group and wherein R3 through R9 are independently --OZ,--C6 M5,--Z,--SiZ3 or --X2, where Z is hydrogen or substituted or unsubstituted phenyl, alkyl, alkenyl or alkynyl; X2 is chlorine, bromine, iodine or fluorine; M is independently at each occurrence Z or X2 ; R3 and R4 may together be an electron pair; two or more of R3, R4, R5 and R6 may be combined together and with one or more of C2, C3 or C4 to form a ring structure and R1 and R2 may be joined together with C1 to form a ring structure; said method comprising reacting a 1-haloalkyl 1-sulfonyl halide with a second compound of the formula: STR4 at a temperature below 25° C. for less than 12 hours where R3, R4 and R5 are as previously described, R10 is R6 as previously described or R11, a radical of the formula: STR5 This invention was made with Government support under CHE 811530801 awarded by the National Science Foundation. The Government has certain rights in this invention.
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- A NOVEL STEREOSELECTIVE SYNTHESIS OF 1,3,5-TRIENES VIA SO2 EXTRUSION FROM SULFOLENES.
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(E)-1,3,5-hexatriene as well as (E,E)-1,3,5-undecatriene and (E,Z)-1,3,5-undecatriene, two natural compounds isolated from the essential oils of Galbanum and Dictyoperis, were stereoselectively synthesized from sulfolenes generated by a retro-Diels-Alder reaction.
- Bloch, R.,Benecou, C.,Guibe-Jampel, E.
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p. 1301 - 1304
(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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- NOUVELLE SYNTHESE DES UNDECATRIENES-1,3,5 NATURELS
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The two natural 1,3,5-undecatrienes have been synthesized starting from pyridazine-1-oxide.The methode allows us to obtain a mixture, in which the 1,3E,5Z isomer predominates.
- Giraudi, E.,Teisseire, P.
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p. 489 - 492
(2007/10/02)
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- Process for the preparation of poly-unsaturated hydrocarbons
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Process for the preparation of poly-unsaturated hydrocarbons, in particular undeca-1,3,5-triene, which comprises reacting a quaternary phosphonium salt with hexanal. The product obtained in accordance with the process of the invention is a useful perfuming ingredient.
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