362052-00-4Relevant articles and documents
Preparation method of organic carboxylic acid
-
Paragraph 0056-0058, (2019/10/15)
The invention discloses a preparation method of organic carboxylic acid. The preparation method comprises the following steps that catalysts, olefins, water and solvents are added into a reaction container; CO is introduced; heating reaction is performed; after the reaction completion, separation is performed to obtain organic carboxylic acid; the catalysts comprise transition metal catalysts, ligands and catalysis assistants; the catalysis assistants comprise Lewis acid salt. The preparation method has the advantages that the dependency on protonic acid in the prior art is avoided; the Lewisacid salt is used as the catalysis assistant, so that the corrosion of a reaction system on equipment can be effectively prevented; the requirements on equipment are lowered. The preparation method has excellent substrate practicability; the operation steps are simple and fast; the reaction conditions are mild and are easy to control; the raw materials are cheap and can be easily obtained; the product yield and the product purity are high; the preparation method is suitable for large-scale industrial production; the normal/iso ratio of reaction products can be regulated and controlled throughthe catalysis assistants; the defects of regulating and controlling the normal/iso ratio of the reaction products by traditional phosphine ligands are overcome; the reaction progress of the reaction is simplified; the cost is favorably reduced.
Visible-Light-Driven External-Reductant-Free Cross-Electrophile Couplings of Tetraalkyl Ammonium Salts
Liao, Li-Li,Cao, Guang-Mei,Ye, Jian-Heng,Sun, Guo-Quan,Zhou, Wen-Jun,Gui, Yong-Yuan,Yan, Si-Shun,Shen, Guo,Yu, Da-Gang
, p. 17338 - 17342 (2019/01/04)
Cross-electrophile couplings between two electrophiles are powerful and economic methods to generate C-C bonds in the presence of stoichiometric external reductants. Herein, we report a novel strategy to realize the first external-reductant-free cross-electrophile coupling via visible-light photoredox catalysis. A variety of tetraalkyl ammonium salts, bearing primary, secondary, and tertiary C-N bonds, undergo selective couplings with aldehydes/ketone and CO2. Notably, the in situ generated byproduct, trimethylamine, is efficiently utilized as the electron donor. Moreover, this protocol exhibits mild reaction conditions, low catalyst loading, broad substrate scope, good functional group tolerance, and facile scalability. Mechanistic studies indicate that benzyl radicals and anions might be generated as the key intermediates via photocatalysis, providing a new direction for cross-electrophile couplings.
Regioselectivity inversion tuned by iron(iii) salts in palladium-catalyzed carbonylations
Huang, Zijun,Cheng, Yazhe,Chen, Xipeng,Wang, Hui-Fang,Du, Chen-Xia,Li, Yuehui
supporting information, p. 3967 - 3970 (2018/04/23)
Impactful regioselectivity control is crucial for cost-effective chemical synthesis. By using cheap and abundant iron(iii) salts, the hydroxycarbonylations of both aromatic and aliphatic alkenes were significantly enhanced in both reactivity and selectivity (iso/n or n/iso up to >99:1). Moreover, Pd-catalyzed carbonylation selectivity can be switched from branched to linear by using different Fe(iii) salts. In addition, similar results were obtained for the carbonylation of secondary alcohols.
Ligand-Controlled Regioselective Hydrocarboxylation of Styrenes with CO2 by Combining Visible Light and Nickel Catalysis
Meng, Qing-Yuan,Wang, Shun,Huff, Gregory S.,Konig, Burkhard
supporting information, p. 3198 - 3201 (2018/03/13)
The ligand-controlled Markovnikov and anti-Markovnikov hydrocarboxylation of styrenes with atmospheric pressure of CO2 at room temperature using dual visible-light-nickel catalysis has been developed. In the presence of neocuproine as ligand, the Markovnikov product is obtained exclusively, while employing 1,4-bis(diphenylphosphino)butane (dppb) as the ligand favors the formation of the anti-Markovnikov product. A range of functional groups and electron-poor, -neutral, as well as electron-rich styrene derivatives are tolerated by the reaction, providing the desired products in moderate to good yields. Preliminary mechanistic investigations indicate the generation of a nickel hydride (H-NiII) intermediate, which subsequently adds irreversibly to styrenes.
Construction of a visible light-driven hydrocarboxylation cycle of alkenes by the combined use of Rh(i) and photoredox catalysts
Murata, Kei,Numasawa, Nobutsugu,Shimomaki, Katsuya,Takaya, Jun,Iwasawa, Nobuharu
supporting information, p. 3098 - 3101 (2017/03/17)
A visible light driven catalytic cycle for hydrocarboxylation of alkenes with CO2 was established using a combination of a Rh(i) complex as a carboxylation catalyst and [Ru(bpy)3]2+ (bpy = 2,2′- bipyridyl) as a photoredox catalyst. Two key steps, the generation of Rh(i) hydride species and nucleophilic addition of π-benzyl Rh(i) species to CO2, were found to be mediated by light.
Nickel-Catalyzed Carboxylation of Benzylic C-N Bonds with CO2
Moragas, Toni,Gaydou, Morgane,Martin, Ruben
supporting information, p. 5053 - 5057 (2016/04/26)
A user-friendly Ni-catalyzed reductive carboxylation of benzylic C-N bonds with CO2 is described. This procedure outperforms state-of-the-art techniques for the carboxylation of benzyl electrophiles by avoiding commonly observed parasitic pathways, such as homodimerization or β-hydride elimination, thus leading to new knowledge in cross-electrophile reactions.
Electrochemical direct carboxylation of benzyl alcohols having an electron-withdrawing group on the phenyl ring: One-step formation of phenylacetic acids from benzyl alcohols under mild conditions
Senboku, Hisanori,Yoneda, Kenji,Hara, Shoji
, p. 6772 - 6776 (2016/01/30)
Electrochemical direct carboxylation of benzyl alcohols having an electron-withdrawing group on the phenyl ring was successfully carried out by constant current electrolysis using an undivided cell equipped with a platinum plate cathode and a magnesium rod anode in DMF in the presence of carbon dioxide. Reductive cleavage of the C-O bond followed by fixation of carbon dioxide efficiently took place at the benzylic position without any additive to give the corresponding phenylacetic acids in good yields in one step under neutral and mild conditions.
Development of a novel electrochemical carboxylation system using a microreactor
Tateno, Hiroyuki,Matsumura, Yoshimasa,Nakabayashi, Koji,Senboku, Hisanori,Atobe, Mahito
, p. 98721 - 98723 (2015/12/05)
We have developed a novel electrochemical carboxylation system for CO2 fixation to benzyl halides using a microreactor. In this system, electrochemical carboxylation of benzyl halides proceeded very efficiently without the use of a sacrificial anode such as a Mg anode to give carboxylated products in excellent yields.
ARYL OR N-HETEROARYL SUBSTITUTED METHANESULFONAMIDE DERIVATIVES AS VANILLOID RECEPTOR LIGANDS
-
, (2013/04/13)
The invention relates to aryl or N-heteroaryl substituted methanesulfonamide derivatives of Formula (I) as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
Aryl or N-heteroaryl Substituted Methanesulfonamide Derivatives as Vanilloid Receptor Ligands
-
, (2013/04/10)
The invention relates to aryl or N-heteroaryl substituted methanesulfonamide derivatives as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
