1572-99-2Relevant articles and documents
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
Motokura, Ken,Fujita, Noriaki,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
, p. 5507 - 5510 (2005)
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.
HYDROGENATION OF α-CYANOACRYLIC ACID AND ITS ESTERS BY ORGANOHYDRIDESILANES
Kolomnikova, G. D.,Prikhodchenko, D. Yu.,Gololobov, Yu. G.
, p. 1282 - 1283 (1992)
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.
Asymmetric base-free michael addition at room temperature with nickel-based bifunctional amido-functionalized N-heterocyclic carbene catalysts
Rao, Mitta Nageswar,Haridas, Meera,Gangwar, Manoj Kumar,Rajakannu, Palanisamy,Kalita, Alok Ch.,Ghosh, Prasenjit
, p. 1604 - 1615 (2015)
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.
Quinazolinone Compound and Application Thereof
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Paragraph 0105-0107; 0541-0543, (2020/11/27)
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.
Regioselective Copper-Catalyzed Oxidative Coupling of α-Alkylated Styrenes with Tertiary Alkyl Radicals
Wang, Cong,Liu, Rui-Hua,Tian, Ming-Qing,Hu, Xu-Hong,Loh, Teck-Peng
supporting information, p. 4032 - 4035 (2018/07/15)
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.
AlCl3 catalyzed coupling of: N-benzylic sulfonamides with 2-substituted cyanoacetates through carbon-nitrogen bond cleavage
Hu, Chen,Hong, Gang,Qian, Xiaofei,Kim, Kwang Rim,Zhu, Xiaoyan,Wang, Limin
supporting information, p. 4984 - 4991 (2017/07/10)
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.
Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation
Kim, Kelly E.,Li, Jiaming,Grubbs, Robert H.,Stoltz, Brian M.
supporting information, p. 13179 - 13182 (2016/10/22)
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.
Thiazole formation through a modified Gewald reaction
Mallia, Carl J.,Englert, Lukas,Walter, Gary C.,Baxendale, Ian R.
supporting information, p. 875 - 883 (2015/08/24)
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.
β-aryl nitrile construction via palladium-catalyzed decarboxylative benzylation of α-cyano aliphatic carboxylate salts
Shang, Rui,Huang, Zheng,Xiao, Xiao,Lu, Xi,Fu, Yao,Liu, Lei
supporting information, p. 2465 - 2472,8 (2020/08/31)
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
Tandem reactions of 1,2-allenic ketones leading to substituted benzenes and α,β-unsaturated nitriles
Zhang, Xinying,Jia, Xuefei,Fang, Liangliang,Liu, Nan,Wang, Jianji,Fan, Xuesen
supporting information; experimental part, p. 5024 - 5027 (2011/11/12)
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.
