- One-pot synthesis of α-alkylated nitriles with carbonyl compounds through consecutive aldol reaction/hydrogenation using a hydrotalcite-supported palladium nanoparticle as a multifunctional heterogeneous catalyst
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α-Alkylation of various nitriles with carbonyl compounds successfully proceeded using a hydrotalcite-supported palladium nanoparticle as a multifunctional catalyst. The alkylated nitriles were formed through aldol reaction at base sites on the hydrotalcite surface followed by hydrogenation by molecular hydrogen on the palladium nanoparticle.
- Motokura, Ken,Fujita, Noriaki,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
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- HYDROGENATION OF α-CYANOACRYLIC ACID AND ITS ESTERS BY ORGANOHYDRIDESILANES
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The C=C bond in α-cyanoacrylic acid is readily hydrogenated by organohydridesilanes in the absence of catalyst.The hydrogenation of α-cyanoacrylate esters requires the presence of acid.Keywords: cyanoacrylic acid, hydrogenation, organohydridesilanes, alkenes, esters of cyanoacrylic acid.
- Kolomnikova, G. D.,Prikhodchenko, D. Yu.,Gololobov, Yu. G.
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- Asymmetric base-free michael addition at room temperature with nickel-based bifunctional amido-functionalized N-heterocyclic carbene catalysts
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A series of nickel-based chiral bifunctional catalysts (1d-3d) with N-heterocyclic carbene (NHC) ligands derived from (1R)-(-)-menthol, (1S)-(-)pinene, and (1R)-(+)-camphor have been successfully designed for asymmetric Michael addition reactions under base-free conditions. The NHC complexes, namely, [1-R-3-{N-(phenylacetamido)}imidazol-2-ylidene]2Ni [R = (1S)-menthyl (1d), (1S)-pinane (2d), and (1R)-isobornyl (3d)], bearing chiral ancillaries on the amido-functionalized side arms of the NHC ligands, performed the bifunctional catalysis of the asymmetric base-free Michael addition reaction of the α-methyl cyano ester substrates ethyl 2-cyanopropanoate (4), isopropyl 2-cyanopropanoate (5), and tert-butyl 2-cyanopropanoate (6) with the activated olefinic substrates methyl vinyl ketone (7) and acrylonitrile (8) in 63-98 % yields with enantiomeric excess (ee) values of 2-75 % at room temperature in 8 h. More interestingly, only the longest of the three catalysts, the menthol derivative 1d, showed significant chiral induction of up to 75 % ee; this has been attributed to the reduction of the steric influence owing to the relatively distant dispositions of the chiral ancillaries from the catalytically active metal center that arise as a consequence of the cis geometries of 1d-3d. A series of nickel-based chiral bifunctional catalysts with N-heterocyclic carbene ligands derived from readily available and inexpensive (1R)-(-)-menthol, (1S)-(-)pinene, and (1R)-(+)-camphor synthons successfully catalyze asymmetric base-free Michael addition reactions under ambient conditions.
- Rao, Mitta Nageswar,Haridas, Meera,Gangwar, Manoj Kumar,Rajakannu, Palanisamy,Kalita, Alok Ch.,Ghosh, Prasenjit
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- Quinazolinone Compound and Application Thereof
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The present invention relates to a series of quinazolinone compounds and applications thereof as PI3Kα inhibitors. In particular, the present invention relates to a compound shown in formula (I) and a tautomer or pharmaceutically acceptable salt thereof.
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Paragraph 0105-0107; 0541-0543
(2020/11/27)
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- Regioselective Copper-Catalyzed Oxidative Coupling of α-Alkylated Styrenes with Tertiary Alkyl Radicals
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A radical-mediated oxidative cross-coupling of readily accessible α-alkylated styrenes with 1,3-dicarbonyl compounds utilizing a combination of Cu(OAc)2 and air as a catalytic system is described. Rather than requiring α-halocarbonyl compounds, this efficient approach enables direct installation of tertiary functionalized alkyl motifs to olefins with simple carbonyl derivatives. The novel protocol is characterized with high allylic selectivities via a competing β-H elimination. Both radical-clock and -trapping experiments provided clear-cut evidence for the intermediacy of an α-keto carbon-centered radical.
- Wang, Cong,Liu, Rui-Hua,Tian, Ming-Qing,Hu, Xu-Hong,Loh, Teck-Peng
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supporting information
p. 4032 - 4035
(2018/07/15)
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- AlCl3 catalyzed coupling of: N-benzylic sulfonamides with 2-substituted cyanoacetates through carbon-nitrogen bond cleavage
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A new cross-coupling reaction of N-benzylic sulfonamides with 2-substituted cyanoacetates for the synthesis of 2-substituted benzylbenzene was reported. In the presence of AlCl3, a broad range of N-benzylic sulfonamides reacted smoothly with 2-substituted cyanoacetates to afford structurally diverse benzylbenzenes in moderate to excellent yields. The conversion could be enlarged to gram-scale efficiently. The practicability of this approach was further manifested in the synthesis of a related bioactive agent with high anti-inflammatory activity.
- Hu, Chen,Hong, Gang,Qian, Xiaofei,Kim, Kwang Rim,Zhu, Xiaoyan,Wang, Limin
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supporting information
p. 4984 - 4991
(2017/07/10)
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- Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation
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A new strategy for the functionalization of sterically hindered terminal olefins is reported. Alkenes bearing quaternary carbons at the allylic or homoallylic position are readily oxidized to the corresponding aldehydes by palladium/copper/nitrite catalysis. A broad range of functional groups including esters, nitriles, silyl ethers, vinylogous esters, ketones, lactones, and β-ketoesters are tolerated under the reaction conditions. The crude aldehyde products can be transformed further, enabling direct conversion of hindered terminal alkenes to various other synthetically useful functional groups, resulting in formal anti-Markovnikov hydroamination, among other transformations.
- Kim, Kelly E.,Li, Jiaming,Grubbs, Robert H.,Stoltz, Brian M.
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supporting information
p. 13179 - 13182
(2016/10/22)
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- Thiazole formation through a modified Gewald reaction
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The synthesis of thiazoles and thiophenes starting from nitriles, via a modified Gewald reaction has been studied for a number of different substrates. 1,4-Dithiane-2,5-diol was used as the aldehyde precursor to give either 2-substituted thiazoles or 2-substituted aminothiophenes depending on the substitution of the α-carbon to the cyano group.
- Mallia, Carl J.,Englert, Lukas,Walter, Gary C.,Baxendale, Ian R.
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supporting information
p. 875 - 883
(2015/08/24)
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- β-aryl nitrile construction via palladium-catalyzed decarboxylative benzylation of α-cyano aliphatic carboxylate salts
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The palladium-catalyzed decarboxylative benzylation of α-cyano aliphatic carboxylate salts with benzyl electrophiles was discovered. This reaction exhibits good functional group compatibility and proceeds under relatively mild conditions. A diverse range of quaternary, tertiary and secondary β-aryl nitriles can be conveniently prepared by this method. Copyright
- Shang, Rui,Huang, Zheng,Xiao, Xiao,Lu, Xi,Fu, Yao,Liu, Lei
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supporting information
p. 2465 - 2472,8
(2020/08/31)
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- Tandem reactions of 1,2-allenic ketones leading to substituted benzenes and α,β-unsaturated nitriles
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One-pot double Michael addition/intramolecular aldol reaction/ decarboxylation of 1,2-allenic ketones with cyanoacetate offers an efficient and convenient approach to highly functionalized benzenes. With 2-substituted cyanoacetates, the reaction proceeds via a different tandem process to afford α,β-unsaturated nitriles effectively.
- Zhang, Xinying,Jia, Xuefei,Fang, Liangliang,Liu, Nan,Wang, Jianji,Fan, Xuesen
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supporting information; experimental part
p. 5024 - 5027
(2011/11/12)
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- Environmentally friendly one-pot synthesis of α-alkylated nitriles using hydrotalcite-supported metal species as multifunctional solid catalysts
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A ruthenium-grafted hydrotalcite (Ru/HT) and hydrotalcite-supported palladium nanoparticles (Pdnano/ HT) are easily prepared by treating basic layered double hydroxide, hydrotalcite (HT, Mg6Al 2(OH)16CO3) with aqueous RuCl 3·n H2O and K2[PdCl4] solutions, respectively, using surface impregnation methods. Analysis by means of X-ray diffraction, and energydispersive X-ray, electron paramagnetic resonance, and X-ray absorption fine structure spectroscopies proves that a monomeric RuIV species is grafted onto the surface of the HT. Meanwhile, after reduction of a surface-isolated PdII species, highly dispersed Pd nanoclusters with a mean diameter of about 70 A is observed on the Pdnano/HT surface by transmission electron microscopy analysis. These hydrotalcite-supported metal catalysts can effectively promote α-alkylation reactions of various nitriles with primary alcohols or carbonyl compounds through tandem reactions consisting of metal-catalyzed oxidation and reduction, and an aldol reaction promoted by the base sites of the HT. In these catalytic α-alkylations, homogeneous bases are unnecessary and the only by-product is water. Additionally, these catalyst systems are applicable to one-pot syntheses of glutaronitrile derivatives.
- Motokura, Ken,Fujita, Noriaki,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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p. 8228 - 8239
(2007/10/03)
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- A convenient procedure for the preparation of alkyl nitriles from alkyl halides. Acetone cyanohydrin as an in situ source of cyanide ion
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A convenient preparation of alkyl nitriles from alkyl halides is described. Acetone cyanohydrin is employed as the source of cyanide ion.
- Dowd,Wilk,Wlostowski
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p. 2323 - 2329
(2007/10/02)
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- Chemistry of Novel Compounds with Multifunctional Carbon Structure. 9. Molecular Design, Synthetic Studies, and NMR Investigation of Several Efficient Chiral Derivatizing Reagents which Give Very Large (19)F NMR Δδ Values in Enantiomeric Excess Determination
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In order to develop efficient ee-determining reagents potentially superior to MTPA (1), some multifunctional compounds 2-5 were rationally designed.From NMR investigations of the analogous diastereomeric derivatives it was found that the chemical shift differences for each pair of diastereomers (Δδ values) for CFPA derivatives 5d-f were approximately five times greater in (19)F NMR spectra and two times greater in 1H NMR spectra than those of 1d-f.Synthesis of the optically pure CFPA, (-)-5a nd (+)-5a, was achieved by nitrosation of each diasteromer of the optically active N-(1-phenylethyl)amides, 5fM and 5fL, followed by thermal decomposition.Various derivatives were prepared by the condensation of 5b and 1b with alcohol and amine nucleophiles, and both ΔδF and ΔδH values were obtained for each compound.The CFPA derivatives 5d-m have proven to be significantly superior for ee determinations when compared to the corresponding MTPA derivatives 1d-m, particularly in compounds having remotely disposed chiral centers.
- Takeuchi, Yoshio,Itoh, Noriaki,Satoh, Toshihiro,Koizumi, Toru,Yamaguchi, Kentaro
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p. 1812 - 1820
(2007/10/02)
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- C-H Bond Activation by Ruthenium(0) Complexes. Isolation of an Active Intermediate in the Ruthenium Catalyzed Aldol and Michael Reactions
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Carbon-hydrogen bond oxidative addition of alkyl cyanoacetate to Ru(C2H4)(PPh3)3 in benzene at room temperature gives mer-RuH(NCCHCOOR)(NCCH2COOR)(PPh3)3 (R=Me, Et) accompanied by the liberation of ethylene.X-Ray structure analysis of the THF adduct (R=Me) reveals that NCCHCOOMe group bonds to ruthenium not through the methine carbon but the cyano group.These complexes react with benzaldehyde and methyl iodide to give alkyl (E)-1-cyanocinnamate and alkyl-2-cyanopropionate, respectively.
- Mizuho, Yuji,Kasuga, Noriko,Komiya, Sanshiro
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p. 2127 - 2130
(2007/10/02)
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- Cobalt Carbonyl Mediated Michael Addition: Direct Synthesis of Esters Containing Other Functional Groups from Activated Olefins
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Hydrocarbalkoxylation of acrylonitrile with stoichiometric amounts of alcohols in the presence of catalytic amounts of Co2(CO)8 and pyridine bases leads to 2,4-dicyano-2-methylbutanoic acid esters.The yield of these Michael adducts shows a maximum as a function of the pyridine/cobalt ratio.Analogues reactions using equimolar amounts of alcohol, acrylonitrile, and an other activated olefin result in products with at least three different functional groups.Acrylonitrile with pyH gives (1-cyanoethyl)cobalt tetracarbonyl, which is proposed to be the key intermediate of the hydrocarbalkoxylation.This complex may be deprotonated to a "Michael donor" anion, i.e. the Michael adducts are most probably formed in a cobalt-mediated way.The above catalytic system promoted also the Michael addition of some C-H acids to activated olefins under atmospheric conditions.
- Sisak, Attila,Ungvary, Ferenc,Marko, Laszlo
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p. 2508 - 2513
(2007/10/02)
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- Reaction of Guanidinium Salts with Alkyl Bromides and Acid Chlorides
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The guanidinium salt 1a reacts with alkyl bromides 2a-g and acid chlorides 2h-k to give the nitriles 3a-g and the acyl cyanides 3h-k, respectively.Acyl isocyanates 4a,b have been obtained from the guanidinium cyanate 1d and the acid chlorides 2h,l.Reaction of the alkyl bromides 2b,c,m,n and acid chlorides 2h,l with the guanidinium thiocyanate 1e affords alkyl thiocyanates 5a-d and acyl isothiocyanates 6a,b, respectively.
- Kantlehner, Willi,Kapassakalidis, Johannis J.,Speh, Peter,Braeuner, Hans-Juergen
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p. 389 - 393
(2007/10/02)
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- Method of preparing α-substituted cyanoacetic acid alkyl esters
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A process for preparing an α-substituted cyanoacetic acid alkyl ester which comprises contacting an unsaturated nitrile of the formula STR1 wherein R2 is a hydrogen atom or a methyl group and R3 is CH2, CHCH3, CHCN, CHC6 H5 or C(CH3)2 with an alcohol of the formula wherein R is a primary, secondary or tertiary saturated alkyl moiety of 1 to 20 carbon atoms and carbon monoxide in the presence of Co2 (CO)8 and an α-substituted pyridine in the absence of hydrogen at an elevated temperature and pressure.
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- Manufacture of 2-cyano-propionate esters
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A process for the manufacture of 2-cyano-propionate esters which comprises hydrogenating in the presence of an hydrogenating catalyst a mixture of a cyano-acetic ester, formaldehyde and a condensation catalyst. Typically ethyl cyano-acetate is treated with formalin or paraform and hydrogen in the presence of palladium on carbon and zinc acetate. Preferably an antioxidant or polymerisation inhibitor is also included in the reaction mixture which also usually includes solvents such as glacial acetic acid or toluene.
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