- (E)-beta,gamma-alkenyl carboxylic acid derivative and preparation method thereof
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The invention discloses an (E)-beta,gamma-alkenyl carboxylic acid derivative and a preparation method thereof. The preparation method disclosed by the invention comprises the following steps: in an organic solvent, under the condition that a nickel catalyst, a dinitrogen ligand, a reducer and an additive exist, carrying out a carboxylation reaction on an allyl alcohol substrate as shown in formula (II) and carbon dioxide. The preparation method disclosed by the invention is high in selectivity, the raw material reagents are easy to get and has high chemical selectivity and region selectivity, and the derivative is high in yield, high in purity, and low in generation cost and is more applicable for industrial production. (Refer to Specification).
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Paragraph 0138-0141
(2017/08/31)
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- Efficient Pd-Catalyzed Regio- and Stereoselective Carboxylation of Allylic Alcohols with Formic Acid
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Formic acid is efficiently used as a C1 source to directly carboxylate allylic alcohols in the presence of a low loading of palladium catalyst and acetic anhydride as additive to afford β,γ-unsaturated carboxylic acids with excellent chemo-, regio-, and stereoselectivity. The reaction proceeds through a carbonylation process with in situ-generated carbon monoxide under mild conditions, avoiding the use of high-pressure gaseous CO. A bisphosphine ligand with a large bite angle (4,5-bis{diphenylphosphino}-9,9-dimethylxanthene, Xantphos) was found to be uniquely effective for this transformation. The regio- and stereoconvergence of this reaction is ascribed to the thermodynamically favored isomerization of the allylic electrophile in the presence of the palladium catalyst.
- Fu, Ming-Chen,Shang, Rui,Cheng, Wan-Min,Fu, Yao
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p. 8818 - 8822
(2017/07/11)
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- Regioselective Ni-Catalyzed Carboxylation of Allylic and Propargylic Alcohols with Carbon Dioxide
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An efficient Ni-catalyzed reductive carboxylation of allylic alcohols with CO2 has been successfully developed, providing linear β,γ-unsaturated carboxylic acids as the sole regioisomer with generally high E/Z stereoselectivity. In addition, the carboxylic acids can be generated from propargylic alcohols via hydrogenation to give allylic alcohol intermediates, followed by carboxylation. A preliminary mechanistic investigation suggests that the hydrogenation step is made possible by a Ni hydride intermediate produced by a hydrogen atom transfer from water.
- Chen, Yue-Gang,Shuai, Bin,Ma, Cong,Zhang, Xiu-Jie,Fang, Ping,Mei, Tian-Sheng
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supporting information
p. 2969 - 2972
(2017/06/07)
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- Ligand-controlled regiodivergent Ni-catalyzed reductive carboxylation of allyl esters with CO2
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A novel Ni-catalyzed regiodivergent reductive carboxylation of allyl esters with CO2 has been developed. This mild, user-friendly, and operationally simple method is characterized by an exquisite selectivity profile that is dictated by the ligand backbone.
- Moragas, Toni,Cornella, Josep,Martin, Ruben
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supporting information
p. 17702 - 17705
(2015/02/19)
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- Taming the carboxyl group for directed carbometalation: Observations on the use of anions, dianions and ester enolates
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Carboxylate anions, dianions and ester enolates provide simultaneous protection and activation for directed carbometalation reactions. Advantage can be taken of the bis-carbanionic character of the intermediate for further controlled C-C bond forming reac
- Desrat, Sandy,Gray, Philip J.,Penny, Matthew R.,Motherwell, William B.
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supporting information
p. 8918 - 8922
(2014/07/22)
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- Enantiodivergent and γ-selective asymmetric allylic amination
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Double agent: The title reaction using the guanidine catalyst 1 can deliver both enantiomers of the product with excellent enantioselectivity by judicious choice of the double bond geometry of the the β,γ-unsaturated carbonyl compound. Computational studies reveal the possible origin of the inversed enantioselectivity, and the potential for enantiodivergent synthesis chiral amine-containing substrates is attractive. Copyright
- Wang, Jianmin,Chen, Jie,Kee, Choon Wee,Tan, Choon-Hong
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supporting information; experimental part
p. 2382 - 2386
(2012/05/19)
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- Regioselective ring opening and isomerization reactions of 3,4-epoxyesters catalyzed by boron trifluoride
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Efficient ring opening of 3,4-epoxyesters with alcohols to produce 4-alkoxy-3-hydroxyesters and their isomerization into 4-ketoesters using boron trifluoride as the catalyst are presented. Both transformations are simple and efficient methods for the synthesis of the above named synthetically useful compounds.
- Izquierdo, Javier,Rodriguez, Santiago,Gonzalez, Florenci V.
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supporting information; experimental part
p. 3856 - 3859
(2011/09/19)
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- Method for regio- and stereoselective synthesis of (E)-Β,γ- unsaturated acids from aldehydes under solvent-free conditions
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Synthesis of (E)-β,-γunsaturated acids from aldehydes with malonic acid has been explored under solvent-free conditions. The modified Knoevenagel condensation reaction with N-methyl morpholine (NMM) as catalyst exhibits highly β,-γ regioselectivity and exclusively E-stereoselectivity. A mechanism accounting for both regio- and stereoselectivity has been proposed and preliminarily studied. Copyright Taylor & Francis Group, LLC.
- Zhang, Shi-Jie,Hu, Wei-Xiao
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experimental part
p. 3093 - 3100
(2010/12/19)
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- (E)-Selective hydrolysis of (E,Z)-α,β-unsaturated nitriles by the recombinant nitrilase AtNIT1 from Arabidopsis thaliana
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From stereoisomeric α,β-unsaturated nitriles (E,Z)-1, the recombinant nitrilase AtNIT1 from Arabidopsis thaliana hydrolyses the (E)-isomers exclusively to the corresponding (E)-carboxylic acids (E)-2 with high specificity. The (E)-selectivity can also be utilised for the preparation of the isomerically pure nitriles (Z)-1. From (E,Z)-2-hydroxycinnamonitrile (E,Z)-3, the otherwise difficult obtainable (Z)-3 was prepared in 66% isolated yield. With β,γ-unsaturated (E,Z)-3-heptenenitrile (E,Z)-4, however, (E)-selectivity was not observed. AtNIT1 exhibits not only diastereoselectivity but also regioselectivity. From a mixture of the four isomers A-D of 3-(2-cyanocyclohex-3-enyl)propenenitrile 6, exclusively isomer D ((E)-cis-6) was hydrolysed to 3-(2-cyanocyclohex-3-enyl)propenoic acid (E)-cis-7, as stated by X-ray crystal structure. Only after complete conversion of D and high enzyme concentrations, isomer C ((E)-trans-6) was hydrolysed to a small extent.
- Effenberger, Franz,Osswald, Steffen
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p. 2581 - 2587
(2007/10/03)
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- SiO2 catalysed expedient synthesis of [E]-3-alkenoic acids in dry media
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Aliphatic aldehydes with α-hydrogens and malonic acid undergo decarboxylative condensation on the surface of SiO2 when subjected to microwave irradiation generating βγ-unsaturated acids in high yields.
- Kumar, H.M. Sampath,Reddy, B.V. Subba,Reddy, E. Jagan,Yadav
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p. 2401 - 2404
(2007/10/03)
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- Improvement on the synthesis of (E)-alk-3-enoic acids
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(E)-Alk-3-enoic acids have been prepared in high yield (85-90%) and excellent stereoselectivity (98-99%) by a modified Knoevenagel condensation of a straight carbon chain aldehyde with malonic acid, in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF) at 100°C, in the presence of piperidinium acetate as catalyst. Condensation of the aldehyde with a monoester of malonic acid, under the above conditions, gave the corresponding ester of (E)-alk-3-enoic acid in high yield (76-82%) and good stereoselectivity (90-92%). Condensation of the aldehyde with cyanoacetic acid gave the β,γ-unsaturated nitrile in moderate yield (35-40%) without stereoselectivity.
- Ragoussis, Nikitas,Ragoussis, Valentine
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p. 3529 - 3533
(2007/10/03)
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- Regioselective Synthesis of β,γ-Unsaturated Acids by the Electrochemical Carboxylation of Allylic Bromides Using a Reactive-metal Anode
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Electrolysis of γ-mono and disubstituted allylic bromides in the presence of atmospheric pressure of carbon dioxide using a platinum cathode and a magnesium anode gave regioselectively the corresponding γ-mono and disubstituted β,γ-unsaturated carboxylic acids in 34-71percent yields.
- Tokuda, Masao,Kabuki, Takashi,Katoh, Yoshitaka,Suginome, Hiroshi
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p. 3345 - 3348
(2007/10/02)
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- Aza- and oxacarbonylations of allyl phosphates catalyzed by rhodium carbonyl cluster. Selective synthesis of β,γ-unsaturated amides, esters, and acids
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Rhodium-catalyzed carbonylation of allyl phosphates under CO (20 atm) at 50 deg C proceeds very efficiently in the presence of amines, alcohols, and water to give the corresponding β,γ-unsaturated amides, esters, and acids, respectively.These carbonylations occur with high regioselectivity at the less substituted carbon of allyl unit to give linear β,υ-unsaturated acid derivatives.
- Imada, Yasushi,Shibata, Ou,Murahashi, Shun-Ichi
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p. 183 - 194
(2007/10/02)
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- Activated alkyl- and allyl-alkali metal reagents: Contrasting behaviour towards ethylene
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Ethylene, hex-1-ene and (+)-α-pinene were readily metallated in methylcyclohexane with the system nBuLi/LiK(OCH2CH2NMe2)2.The regioselectivity of the reaction of metallated hex-1-ene and (+)-α-pinene with CO2 could be substantially modified by the addition of Mg(OCH2CH2OEt)2.Addition of the latter also solubilizes the organometallic reagents.The allylmetallic products from the metallation of hex-1-ene and α-pinene added to ethylene under mild conditions.Whereas up to four molecules of ethylene added to metallated hex-1-ene, only one or two, depending on the reaction ratios, added to metallated α-pinene.Similar reactions involving use of a variety of other strong bases such as nBuLi/tC5H11OK and nBuM (M = Li, Na, K), with and without added TMEDA, indicated that the presence of a tertiary amine, apart from assisting the metallation reaction, is essential for the occurrence of the addition.
- Screttas, Constantinos G.,Steele, Barry R.
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p. 163 - 170
(2007/10/02)
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- An electrochemical approach to some insect pheromones with (E)-alkene moiety
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An easy access to some Lepidopteran pheromones containing (E)-alkene moiety via anodic oxidation of a partially neutralized mixture of trans-3-alkenoic acids and methyl hydrogen carboxylates has been described.
- Singh, Krishna Nand,Singh, Manorama,Misra, Ram Achal
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p. 431 - 434
(2007/10/02)
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- Oxidative Cleavage of Indane-1,2,3-trione-Ene Adducts; a Convenient Synthesis of Allyl and Allenyl Carboxylic Acids
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The ene adducts formed by the thermal reaction of indane-1,2,3-trione with olefins or terminal alkynes are cleaved in good yield by reaction with periodic acid in dry diethyl ether.Thereby the 2-hydroxyindane-1,2-dione moiety in the adduct is replaced by a CO2H group; hence indane-1,2,3-trione is a masked equivalent of carbon dioxide in the ene reaction.The allyl or allenyl carboxylic acid may be separated from the co-products (phthalic acid and anhydride) by extraction into hexane.
- Gill, G. Bryon,Idris, Muhammad S. Hj.,Kirollos, Kirollos S.
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p. 2367 - 2370
(2007/10/02)
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- MODIFIED KNOEVENAGEL CONDENSATIONS. SYNTHESIS OF (E)-3-ALKENOIC ACIDS.
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Condensation of aliphatic aldehydes with a three molar excess of malonic acid and 0.001 mole piperidinium acetate in refluxing xylene, with continuous removal of the water formed, gave almost exclusively (E)-3-alkenoic acids, in good yield (60-85percent) and of high stereochemical purity (95-99percent).
- Ragoussis, Nikitas
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- INDANE-1,2,3-TRIONE ; A HIGHLY REACTIVE ENOPHILE
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Among the 1,2,3-tricarbonyl systems investigated, indane-1,2,3-trione has been found to be a particularly reactive enophile.Cleavage of the adducts with periodic acid affords allyl carboxylic acids.Both addition and cleavage reactions are essentially quantitative.
- Gill, G. Bryon,Kirollos, Kirollos S.
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p. 1399 - 1402
(2007/10/02)
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- A CONVENIENT METHOD FOR THE SYNTHESIS OF (E)-3-ALKENOIC ACIDS BY A REGIO- AND STEREOSELECTIVE REACTION OF β-VINYL-β-PROPIOLACTONE WITH ORGANOCOPPER REAGENTS
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β-Vinyl-β-propiolactone reacts regio- and stereoselectively with Grignard reagents in the presence of copper(I) catalyst or with diorganocuprates to afford (E)-3-alkenoic acids in high yields.
- Sato, Toshio,Takeuchi, Masashi,Itoh, Toshiyuki,Kawashima, Masatoshi,Fujisawa, Tamotsu
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p. 1817 - 1820
(2007/10/02)
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