- SYNTHESIS OF THE TWO ISOMERS OF THE POTENTIAL SEX PHEROMONE OF THAUMETOPOEA PITYOCAMPA (LEPIDOPTERA, NOTODONTIDAE) AND RELATED MODEL COMPOUNDS
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The synthesis of the major component of the sex pheromone secretion of the processionary moth, Thaumetopoea pityocampa (Denis and Schiff.) (Lepidoptera, Notodontidae), (Z)-13-hexadecen-11-ynyl acetate (1), the corresponding (E)-isomer (2) and the four structurally related model compounds (Z/E,Z,Z)-5,9,13-hexadecatrienyl acetate (3), (Z/E,Z,Z)-3,7,11-hexadecatrienyl acetate (4), (Z/E,E,Z)-7,9,13-hexadecatrienyl acetate (5) and (Z)-7-hexadecen-5-ynyl acetate (6) is described.
- Camps, Francisco,Coll, Jose,Canela, Ramon,Guerrero, Angel,Riba, Magi
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Read Online
- Synthesis of 9- and 12-nitro conjugated linoleic acid: Regiospecific isomers of naturally occurring conjugated nitrodienes
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Conjugated diene-containing fatty acids (rumenic and rumelenic acids) are major substrates for nitration under physiological conditions. Their nitrated products are present in human urine. These nitrodiene-containing lipid electrophiles contain a strongly electron-withdrawing pair of conjugated double bonds amenable to nucleophilic attack in biological milieu, which affords them pluripotent signaling capabilities. We report synthetic methods to obtain useful quantities of three main biological nitrated fatty acids (9- and 12-nitro-conjugated linoleic acids and 9-nitro-conjugated linolenic acid) in six or seven steps from commercially available starting materials, for biological evaluation of these naturally occurring biomolecules.
- Woodcock, Steven R.,Salvatore, Sonia R.,Freeman, Bruce A.,Schopfer, Francisco J.
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supporting information
(2021/09/13)
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- PROCESS FOR PREPARING A 5-ALKEN-1-YNE COMPOUND, (6Z)-1,1-DIALKOXY-6-NONEN-2-YNE COMPOUND, (2E,6Z)-2,6-NONADIENAL AND (2E)-CIS-6,7-EPOXY-2-NONENAL, AND 1,1-DIALKOXY-6-NONEN-2-YNE COMPOUND
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The object of the present invention is to provide a process for preparing a 5-alken-1-yne compound efficiently at low costs and a process for preparing (2E,6Z)-2,6-nonadienal by making use of the aforesaid process for preparing the 5-alken-1-yne compound. There is provided a process for preparing a 5-alken-1-yne compound of the following formula (4): Y-Z-CR1═CR2—(CH2)2—C≡CH (4) in which Y in formula (4) represents a hydrogen atom or a hydroxyl group, the process comprising at least steps of: subjecting (i) an alkenylmagnesium halide compound prepared from a haloalkene compound of the following formula (1): Y-Z-CR1═CR2—(CH2)2-X1 (1) and (ii) an alkyne compound of the following formula (2): X2=C≡C—Si(R3)(R4)(R5) (2) to a coupling reaction to form a silane compound of the following formula (3): Y-Z-CR1═CR2—(CH2)2—C≡C—Si(R3)(R4)(R5) (3); and subjecting the silane compound (3) to a desilylation reaction to form the 5-alken-1-yne compound (4).
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Paragraph 0175-0179
(2020/02/27)
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- PROCESS FOR PREPARING (E2)-CIS-6,7-EPOXY-2-NONENAL
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To provide an industrial and economical process for preparing (E2)-cis-6,7-epoxy-2-nonenal.SOLUTION: The present invention provides a process for preparing (E2)-cis-6,7-epoxy-2-nonenal, comprising at least steps of: subjecting (Z3,Z6)-3,6-nonadien-1-ol to oxidation, to form (E2,Z6)-2,6-nonadienal; and epoxidizing the resulting (E2,Z6)-2,6-nonadienal to form (E2)-cis-6,7-epoxy-2-nonenal.SELECTED DRAWING: None
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Paragraph 0075-0080
(2020/04/02)
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- PROCESS FOR PREPARING (E2)-CIS-6,7-EPOXY-2-NONENAL
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The object of the present invention is to provide an industrial and economical process for preparing (E2)-cis-6,7-epoxy-2-nonenal of the following formula (3):The present invention provides a process for preparing (E2)-cis-6,7-epoxy-2-nonenal (3), comprising at least steps of: subjecting (Z3,Z6)-3,6-nonadien-1-ol of the following formula (1) to oxidation:to form (E2,Z6)-2,6-nonadienal of the following formula (2); andepoxidizing the resulting (E2,Z6)-2,6-nonadienal to form the aforesaid (E2)-cis-6,7-epoxy-2-nonenal (3).
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Paragraph 0080-0085
(2020/03/09)
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- PROCESS FOR PREPARING (E2,Z6)-2,6-NONADIENAL
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The object of the present invention is to provide an industrial and economical process for preparing (E2,Z6)-2,6-nonadienal of the following formula (4): The present invention provides a process for preparing (E2,Z6)-2,6-nonadienal (4), comprising at least steps of: subjecting (Z3,Z6)-3,6-nonadien-1-ol of the following formula (1): to oxidation with a sulfoxide compound of the following formula (2): [in-line-formulae]CH3(R′)S═O??(2)[/in-line-formulae]in which R1 represents a monovalent hydrocarbon group having from 1 to 12 carbon atoms,in the presence of a sulfur trioxide complex and an amine compound of the following formula (3): [in-line-formulae]N(R2)(R3)(R4)??(3)[/in-line-formulae]in which R2, R3, and R4 each independently represent a monovalent hydrocarbon group having from 1 to 12 carbon atoms, or R3 and R4 may be bonded to each other to form a divalent hydrocarbon group having from 3 to 12 carbon atoms, R3-R4,to form the aforesaid (E2,Z6)-2,6-nonadienal (4).
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Paragraph 0061-0066
(2020/03/09)
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- PROCESS FOR PREPARING (2E,6Z)-2,6-NONADIENAL AND A PROCESS FOR PREPARING (2E)-CIS-6,7-EPOXY-2-NONENAL
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Provided herein are convenient and efficient processes for preparing (2E,6Z)-2,6-nonadienal and (2E)-6,7-epoxy-2-nonenal with a reduced number of steps. For instance, provided herein is a process for preparing (2E,6Z)-2,6-nonadienal, including at least steps of subjecting a (6,6-dialkoxy-4-hexenylidene)triarylphosphorane compound of the general formula: Ar3P═CH(CH2)2CH═CHCH(OR1)(OR2) to a Witting reaction with propanal to form a 1,1-dialkoxy-(6Z)-2,6-nonadiene compound of the general formula (6); and subjecting the 1,1-dialkoxy-(6Z)-2,6-nonadiene compound to hydrolysis to form (2E,6Z)-2,6-nonadienal. Also provided is a process for preparing (2E)-cis-6,7-epoxy-2-nonenal of the formula (8), comprising a step of subjecting (2E,6Z)-2,6-nonadienal thus obtained to epoxidation to form (2E)-cis-6,7-epoxy-2-nonenal.
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- Synthesis method of aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenal of Aromia bungii
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The invention relates to a synthesis method of aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenal of Aromia bungii, which belongs to the field of pharmaceutical synthesis. The synthesis method comprises the following steps: taking 1, 4-butanediol as a raw material, singly protecting diol with DHP (dihexylphthalate) and then oxidizing TEMPO (tetramethylpiperidine oxide) into 4-((tetrahydro-2H-pyran-2-base) oxy) butyraldehyde; performing a Wittig reaction, so as to obtain (Z)-2-(hepta-4- alkene-1-base-oxy) tetrahydro-2H-pyran; removing the protection of the DHP and oxidizing TEMPO, so as to obtain (Z)-4-heptenal; performing a Wittig reaction, so as to obtain (2E, 6Z)-nona-2, 6-heptadienal; finally, performing epoxidation, so as to obtain the aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenalof the Aromia bungii. The total yield is 6.5%. In the synthesis method, the 1, 4-butanediol with low cost is taken as the starting raw material; the synthesis method has the advantages of being simple in operation and mild in conditions, therefore, the synthesis method is suitable for large-scale preparation.
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Paragraph 0052; 0053; 0054; 0055; 0056; 0057; 0058; 0059
(2019/05/08)
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- Process for preparing (2e,6z)-2,6-nonadienal and a process for preparing (2e)-cis-6,7-epoxy-2-nonenal
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The object of the invention is to provide convenient and efficient processes for preparing (2E,6Z)-2,6-nonadienal and (2E)-6,7-epoxy-2-nonenal with a reduced number of steps. The present invention provides a process for preparing (2E,6Z)-2,6-nonadienal, comprising at least steps of subjecting a (6,6-dialkoxy-4-hexenylidene)triarylphosphorane compound of the general formula: Ar3P=CH(CH2)2CH=CHCH(OR)(OR) to a Witting reaction with propanal to form a 1,1-dialkoxy-(6Z)-2,6-nonadiene compound of the general formula (6); and subjecting the 1,1-dialkoxy-(6Z)-2,6-nonadiene compound to hydrolysisto form (2E,6Z)-2,6-nonadienal. Also provided is a process for preparing (2E)-cis-6,7-epoxy-2-nonenal of the formula (8), comprising a step of subjecting (2E,6Z)-2,6-nonadienal thus obtained to epoxidation to form (2E)-cis-6,7-epoxy-2-nonenal.
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Paragraph 0119-0121-0131
(2019/12/25)
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- An Engineered Alcohol Oxidase for the Oxidation of Primary Alcohols
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Structure-guided directed evolution of choline oxidase has been carried out by using the oxidation of hexan-1-ol to hexanal as the target reaction. A six-amino-acid variant was identified with a 20-fold increased kcat compared to that of the wild-type enzyme. This variant enabled the oxidation of 10 mm hexanol to hexanal in less than 24 h with 100 % conversion. Furthermore, this variant showed a marked increase in thermostability with a corresponding increase in Tm of 20 °C. Improved solvent tolerance was demonstrated with organic solvents including ethyl acetate, heptane and cyclohexane, thereby enabling improved conversions to the aldehyde by up to 30 % above conversion for the solvent-free system. Despite the evolution of choline oxidase towards hexan-1-ol, this new variant also showed increased specific activities (by up to 100-fold) for around 50 primary aliphatic, unsaturated, branched, cyclic, benzylic and halogenated alcohols.
- Heath, Rachel S.,Birmingham, William R.,Thompson, Matthew P.,Taglieber, Andreas,Daviet, Laurent,Turner, Nicholas J.
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p. 276 - 281
(2019/01/04)
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- One-Step Bioconversion of Fatty Acids into C8-C9 Volatile Aroma Compounds by a Multifunctional Lipoxygenase Cloned from Pyropia haitanensis
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The multifunctional lipoxygenase PhLOX cloned from Pyropia haitanensis was expressed in Escherichia coli with 24.4 mg·L-1 yield. PhLOX could catalyze the one-step bioconversion of C18-C22 fatty acids into C8-C9 volatile organic compounds (VOCs), displaying higher catalytic efficiency for eicosenoic and docosenoic acids than for octadecenoic acids. C20:5 was the most suitable substrate among the tested fatty acids. The C8-C9 VOCs were generated in good yields from fatty acids, e.g., 2E-nonenal from C20:4, and 2E,6Z-nonadienal from C20:5. Hydrolyzed oils were also tested as substrates. The reactions mainly generated 2E,4E-pentadienal, 2E-octenal, and 2E,4E-octadienal from hydrolyzed sunflower seed oil, corn oil, and fish oil, respectively. PhLOX showed good stability after storage at 4 °C for 2 weeks and broad tolerance to pH and temperature. These desirable properties of PhLOX make it a promising novel biocatalyst for the industrial production of volatile aroma compounds.
- Zhu, Zhu-Jun,Chen, Hai-Min,Chen, Juan-Juan,Yang, Rui,Yan, Xiao-Jun
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p. 1233 - 1241
(2018/02/19)
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- A nine carbon homologating system for skip-conjugated polyenes
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Ozonolysis of Z,Z,Z-cylonona-1,4,7-triene leads to a 1,9-difunctionalised Z,Z-3,6-nonadiene which is readily converted into a range of polyunsaturated pheromones and fatty acids.
- Mustafa, Hussein H.,Baird, Mark S.,Al Dulayymi, Juma'A R.,Tverezovskiy, Viacheslav V.
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- Easy access to aroma active unsaturated γ-lactones by addition of modified titanium homoenolate to aldehydes
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The homo-Reformatsky reaction, in which a metal homoenolate of an ester is added to an aldehyde, was adapted to produce γ-lactones from unsaturated, enolizable aldehydes. By use of titanium homoenolate, 11 different γ-lactones were synthesized in one step with moderate to good yields from readily available aldehydes. In particular, this procedure allowed the rapid preparation of a series of C12 unsaturated γ-lactones differing in the position and configuration of the double bond. These reference compounds will be used to identify previously unknown lactones in butter oil. The chromatographic, spectral, and sensory descriptions of the synthesized lactones are provided.
- Frerot, Eric,Bagnoud, Alain
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experimental part
p. 4057 - 4061
(2011/10/31)
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- A study of 1,5-hydrogen shift and cyclization reactions of an alkali isomerized methyl linolenoate
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Heating a mixture formed by alkali isomerization of methyl linolenoate (1) produces a complex mixture with the bicyclic hexahydroindenoic esters 4β-(7-methoxycarbonylheptyl)-5α-methyl-2,3,3aα,4,5, 7aαhexahydroindene (CL5) and 4β-ethyl-5α-(6-methoxycarbonylhexyl)-2,3,3aα,4,5, 7aα-hexahydroindene (CL6) as main components. Similar isomerization reactions of three synthetic model compounds, methyl 9Z,13E,15Z-octadecatrienoate (2), 9Z,14E,16E-octadecatrienoate (4) and 9Z,11E,15Z-octadecatrienoate (5) corroborated the results obtained with alkali isomerized methyl linolenoate.
- Matikainen, Jorma,Kaltia, Seppo,Ala-Peijari, Maija,Petit-Gras, Ninna,Harju, Kirsi,Heikkil?, Jaakko,Yksj?rvi, Raija,Hase, Tapio
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p. 567 - 573
(2007/10/03)
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- Two carbon homologated α,β-unsaturated aldehydes from alcohols using the in situ oxidation-Wittig reaction
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The in situ oxidation-Wittig reaction, followed by subsequent hydrolysis, has been applied to the conversion of primary alcohols into α,β -unsaturated aldehydes. This conversion, which proceeds via the intermediacy of the homologated unsaturated dioxolanes, gives good to excellent yields with a range of benzylic alcohols and heterocyclic methanols.
- Reid, Mark,Rowe, David J.,Taylor, Richard J. K.
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p. 2284 - 2285
(2007/10/03)
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- Direct preparation of (Z,Z)-1,4-dienic units with a new C6 homologating agent: Synthesis of α-linolenic acid
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Syntheses of two C6 homologating agents 2a and 2f are described. These agents allow direct access to the (Z,Z)-1,4-diene unit 3, a moiety present in a wide number of natural compounds. Compound 2a is prepared in 40% overall yield by selective epoxidation of methoxycyclohexa-1,4-diene followed by oxidative ring cleavage and transatalization. Compound 2f is obtained in 90% yield by a one-step oxidative dimerization of phosphonium salt 1. A short synthetic application of these two new C6 homologating agents to the synthesis of α-linolenic acid is described.
- Sandri,Viala
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p. 271 - 275
(2007/10/02)
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- The influence of glutathione and detoxifying enzymes on DNA damage induced by 2-alkenals in primary rat hepatocytes and human lymphoblastoid cells
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The reaction of 2-alkenals with GSH to form GSH conjugates by Michael addition is a major detoxification pathway. The reaction proceeds at a much higher rate under catalysis by glutathione S-transferase (GST) than the non- enzymatic reaction. Oxidation of 2-alkenals to the corresponding acids by cytosolic and microsomal fraction of rat liver also contributes to detoxification. Primary rat hepatocytes rich in GSH and proficient for GST and other metabolizing enzymes consume much more alkenal than human lymphoblastoid cells (Namalva cells), that are poor in GSH and in metabolic activities. In Namalva cells DNA single strand breaks were induced by much lower concentrations of acrolein, crotonaldehyde and (E)-2-hexenal than in primary rat hepatocytes. In both cell systems intracellular GSH depletion by 2-alkenals proceeds in a dose dependent manner, approaching about 20% of pretreatment level before DNA damage becomes detectable. GSH conjugates of (E)-2-hexenal and (2E, 6Z)-2,6-nonadienal induce DNA damage in Namalva cells at high concentrations (1.5 mM). In the absence of GSH these conjugates decompose slowly into aldehyde and GSH. Although the rate of decomposition is only about 10-4 times that of Michael adduct formation, such GSH conjugates could potentially function as transport molecules for 2-alkenals, if they reach tissues low in GSH and GST.
- Eisenbrand,Schuhmacher,Golzer
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- An Isotopic Study (2H and 18O) of the Enzymatic Conversion of Linoleic Acid into Colneleic Acid with Carbon Chain Fracture: the Origin of Shorter Chain Aldehydes
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Contrary to earlier reports, the divinyl 9-ether oxygen of colneleic acid is shown by experiment with 18O2 to originate from oxygen, not water.Using -9(S)-hydroperoxyoctadeca-10(E),12(Z)-dienoic acid, made enzymatically from synthetic linoleic acid, it is found that the distribution of deuterium as determined by NMR and mass spectrometry in the fractured carbon chain of colneic acid formed by potato enzyme, is consistent with the intervention of an epoxy carbonium ion intermediate.Though divinyl acids such as colneleic and colnelenic acid give the expected shorter chain aldehydes on treatment with aqueous acid, it is likely that the latter are formed in most plants by trapping of a monovinyl oxonium ion rather than by rehydration of colneleic and colnelenic acid.
- Crombie, Leslie,Morgan, David O.,Smith, Elisabeth H.
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p. 567 - 575
(2007/10/02)
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- MAGNESIUM-OPPENAUER OXIDATION OF ALCOHOLS TO ALDEHYDES AND KETONES
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Using a magnesium-Oppenauer oxidation aldehydes and ketones are prepared from halomagnesium alkoxides, which in turn are the products of Grignard reactions.
- Byrne, Brian,Karras, Michael
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p. 769 - 772
(2007/10/02)
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- A New Synthesis of Nona-2E,6Z-dienal
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Monosodio ethyl malonate on alkylation with 1-bromo-pent-2-yne (III) furnishes the diester (IV) which on decarbethoxylation with NaCl/DMSO, followed by LAH/EtOH reduction of the resultant ester (V), yields the carbinol (VI).Hydrogenation of VI in the presence of Lindlar's catalyst produces hept-4Z-en-1-ol (VII), which on pyridinium chlorochromate oxidation gives the aldehyde (VIII).Wittig-Horner reaction on VIII using ethyl diethylphosphonoacetate produces the dienoate (IX), which on LAH/EtOH reduction followed by oxidation with Corey's reagent, affords the title compound(I).
- Vig, O. P.,Sharma, M. L.,Gauba, Rita
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p. 313 - 314
(2007/10/02)
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- Palladium-Catalyzed Arylation and Vinylation of 1,4-Dienes
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Bromo- or iodobenzene has been reacted with 1,4-pentadiene, (Z)- or (E)-1,4-hexadiene, and 2-methyl-1,4-pentadiene in the presece of piperidine and a palladium acetate-tri-o-tolylphosphine catalyst. 1-Phenyl-5-piperidino-3-alkenes are major reaction produ
- Bender, Diana D.,Stakem, F. Gregory,Heck, Richard F.
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p. 1278 - 1284
(2007/10/02)
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