- A Unified Strategy for the Synthesis of Difluoromethyl- And Vinylfluoride-Containing Scaffolds
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Here, we report a general method for the synthesis of quaternary and tertiary difluoromethylated compounds and their vinylfluoride analogues. The strategy, which relies on a two-step sequence featuring a C-selective electrophilic difluoromethylation and either a palladium-catalyzed decarboxylative protonation or a Krapcho decarboxylation, is practical, scalable, and high yielding. Considering the generality of the method and the attractive properties offered by the difluoromethyl group, this approach provides a valuable tool for late-stage functionalization and drug development.
- Duchemin, Nicolas,Buccafusca, Roberto,Daumas, Marc,Ferey, Vincent,Arseniyadis, Stellios
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supporting information
p. 8205 - 8210
(2019/10/16)
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- Method for catalytically oxidizing amine to be synthesized into amide through dipyridyl-type manganese catalyst
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The invention discloses a methodfor catalytically oxidizing amine to be synthesized into amide througha dipyridyl-type manganese catalyst. According to the method, a dipyridyl manganese complex formedafter coordination of a dipyridyl-type complex and cheap metal manganese serves as the catalyst, clean and environment-friendly hydrogen peroxide serves as an oxidizing agent, oxidation of N ortho-position sp3 C-H bonds catalyzed by the cheap metal manganese is achieved, and the amine is directly oxidized to obtain the amide. Compared with existing methods, the method has the advantages that theadopted catalyst is low in price, the preparing method is simple, raw materials are easy to obtain, the use level of the catalyst is low, the substrate range is wide, the reaction condition is mild, the operation is simple and environmentally friendly, the reaction time is short, the yield is high, the selectivity is high, and the industrialization cost is low.
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Paragraph 0017-0027; 0052-0054
(2019/06/30)
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- Preparation method of aniracetam
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The invention belongs to the field of medicinal chemistry, and in particular relates to a preparation method of aniracetam. According to the preparation method of the aniracetam provided by the invention, a mixed acid anhydride intermediate is firstly generated by p-methoxybenzoic acid and pivaloyl chloride, and then the mixed acid anhydride intermediate reacts with 2-pyrrolidone to form a targetproduct, namely aniracetam. Therefore, the preparation method of the aniracetam has the advantages that the reaction steps are short, the reaction yield and the product purity are relatively high, rawmaterials are low in cost and easy to obtain, the operation is simple, and the method is suitable for large-scale industrial production and the like.
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Paragraph 0018; 0042-0055
(2019/04/04)
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- Catalytic synthesis method of Aniracetam
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The invention belongs to the technical field of drug synthesis, and in particular relates to a catalytic synthesis method of Aniracetam. The catalytic synthesis method comprises the steps as follows:adding an organic solvent, p-methoxybenzoic acid, 2-pyrrolidone and a boric acid catalyst into a reaction vessel, reacting completely, and performing post-treatment to obtain Aniracetam. The catalyticeffect of the boric acid catalyst is remarkable, and the catalyst itself is cheap and easily available, thereby producing high economic efficiency. The catalytic synthesis method has high atomic utilization rate, and the by-product produced by the method is water, which causes no pollution to the environment. The catalytic synthesis method is easy to operate, and the reaction yield and product purity are high. In summary, the catalytic synthesis method of Aniracetam adopts a green environmentally-friendly preparation process, which is low-cost and especially suitable for large-scale industrial production. Thereby, the method of the invention has a broad application prospect and good market potential.
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Paragraph 0058; 0059; 0061; 0062; 0063-0073
(2019/05/08)
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- CuCl/TMEDA/nor-AZADO-catalyzed aerobic oxidative acylation of amides with alcohols to produce imides
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Although aerobic oxidative acylation of amides with alcohols would be a good complement to classical synthetic methods for imides (e.g., acylation of amides with activated forms of carboxylic acids), to date, there have been no reports on oxidative acylation to produce imides. In this study, we successfully developed, for the first time, an efficient method for the synthesis of imides through aerobic oxidative acylation of amides with alcohols by employing a CuCl/TMEDA/nor-AZADO catalyst system (TMEDA = teramethylethylendiamine; nor-AZADO = 9-azanoradamantane N-oxyl). The proposed acylation proceeds through the following sequential reactions: aerobic oxidation of alcohols to aldehydes, nucleophilic addition of amides to the aldehydes to form hemiamidal intermediates, and aerobic oxidation of the hemiamidal intermediates to give the corresponding imides. This catalytic system utilizes O2 as the terminal oxidant and produces water as the sole by-product. An important point for realizing this efficient acylation system is the utilization of a TMEDA ligand, which, to the best of our knowledge, has not been employed in previously reported Cu/ligand/N-oxyl systems. Based on experimental evidence, we consider that plausible roles of TMEDA involve the promotion of both hemiamidal oxidation and regeneration of an active CuII-OH species from a CuI species. Here promotion of hemiamidal oxidation is particularly important. Employing the proposed system, various types of structurally diverse imides could be synthesized from various combinations of alcohols and amides, and gram-scale acylation was also successful. In addition, the proposed system was further applicable to the synthesis of α-ketocarbonyl compounds (i.e., α-ketoimides, α-ketoamides, and α-ketoesters) from 1,2-diols and nucleophiles (i.e., amides, amines, and alcohols).
- Kataoka, Kengo,Wachi, Keiju,Jin, Xiongjie,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-Ya,Mizuno, Noritaka,Yamaguchi, Kazuya
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p. 4756 - 4768
(2018/06/07)
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- Preparation method of aniracetam
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The invention relates to the field of medicinal chemistry and particularly relates to a preparation method of aniracetam. The synthesis route of aniracetam is shown in the description.
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Paragraph 0036-0049
(2018/05/24)
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- Zirconium-catalysed N-acylation of lactams using unactivated carboxylic acids
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A large number of chemicals including surfactants, nootropic drugs and pesticides contain an N-acylated lactam moiety in their molecular structure. In this work, the direct, catalytic N-acylation of a number of lactams with various unactivated carboxylic
- Hulsbosch, Joris,Claes, Laurens,De Vos, Dirk E.
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supporting information
p. 1646 - 1650
(2018/04/06)
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- Palladium-Catalyzed Hydroamidocarbonylation of Olefins to Imides
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Carbonylation reactions allow the efficient synthesis of all kinds of carbonyl-containing compounds. Here, we report a straightforward synthesis of various imides from olefins and CO for the first time. The established hydroamidocarbonylation reaction affords imides in good yields (up to 90%) and with good regioselectivity (up to 99:1) when applying different alkenes and amides. The synthetic potential of the method is highlighted by the synthesis of Aniracetam by intramolecular hydroamidocarbonylation.
- Li, Haoquan,Dong, Kaiwu,Neumann, Helfried,Beller, Matthias
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supporting information
p. 10239 - 10243
(2015/09/01)
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- A process for the purification of aniracetam by crystallisation from aqueous solutions
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An efficient process for the purification of aniracetam is disclosed by crystallisation from hot aqueous solutions in which the aqueous solution contains equal to or less than 50% by volume of alcohol.
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Paragraph 0018
(2014/10/16)
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- Direct N-acylation of lactams, oxazolidinones, and imidazolidinones with aldehydes by Shvo's catalyst
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Direct N-acylation of lactams, oxazolidinones, and imidazolidinones was achieved with aldehydes by Shvo's catalyst without using any other stoichiometric reagent. The N-acylations with α,β-unsaturated aldehydes were achieved with excellent yields.
- Zhang, Jian,Hong, Soon Hyeok
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supporting information
p. 4646 - 4649
(2012/10/29)
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- [11C]/(13C)carbon monoxide in palladium-mediated synthesis of imides
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[11C]Carbon monoxide in low concentration with palladium(0) complexes (in the range of 5 μmol) and aryl halides (about 10 μmol) were used in the synthesis of the 11C-labelled imides, thalidomide, N-phthaloyl-L-glutamic acid, N-phthaloylhexane and aniracetam. The labellings were performed with ring closure reactions except in the case of aniracetam. These imides were obtained in nearly quantitative radiochemical yields, calculated from the [11C]carbon monoxide, with specific radioactivities between 70-600 GBq μmol-1. The radiochemical purity of the LC-purified products exceeded 98%. N-(13C)Phthaloyl-L-glutamic acid 2 was produced to verify the position of the label (δ 167.5 ppm) with 13C NMR, and this also indicates that the discussed approach is valuable for labelling with other carbon isotopes. In a typical experiment starting with 2.8 GBq of [11C]carbon monoxide, 0.6 GBq of HPLC-purified [11C]-N-phthaloyl-L-glutamic acid 2 was obtained within 40 minutes from the start of the carbonylation reaction (84% decay-corrected radiochemical yield).
- Karimi,Kihlberg,Langstroem
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p. 1528 - 1531
(2007/10/03)
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- Oxidation of N-acyl-pyrrolidines to imides with CrO3·3,5- dimethylpyrazole
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N-Acyl-pyrrolidones are easily obtained by treatment of N-acyl- pyrrolidines with CrO33,5-dimethylpyrazole complex (CrO33,5-DMP) at room temperature.
- Blay, Gonzalo,Cardona, Luz,Garcia, Begona,Garcia, Cristina L.,Pedro, Jose R.
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p. 8257 - 8260
(2007/10/03)
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- 1-(P-Methoxy p-hydroxy, and p-benzyloxy benzoyl)-2-pyrrolidinones
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1-(p-methoxybenzoyl)-2-pyrrolidinone and intermediates useful in its preparation are described. The 1-(p-methoxybenzoyl)-2-pyrrolidinone is useful in the prevention of cerebral insufficiency.
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