78593-46-1Relevant articles and documents
Synthesis and Reactions of 3,3-Difluoro-2- exo-methylidene Indolines
Zeidan, Nicolas,Zambri, Matthew,Unger, Sven,Dank, Christian,Torelli, Alexa,Mirabi, Bijan,Lautens, Mark
, p. 3688 - 3691 (2020)
A dearomative electrophilic fluorination of 2-methylindoles is reported, delivering 3,3-difluoroindolines bearing an exomethylidene. The model substrate was synthesized on up to a 20 mmol scale and was purified by a practical recrystallization as a crystalline bench-stable, yet reactive solid. The olefin is amphoteric and can react both as a nucleophile and as an electrophile. A wide range of metal-free, palladium, rhodium, and copper reactions was explored, forming new C-H, C-B, C-C (alkyl and aryl), C-N, C-O, C-P, and C-S bonds.
Synthesis of functionalized indoles via palladium-catalyzed cyclization of N-(2-allylphenyl) benzamide: A method for synthesis of indomethacin precursor
Chang, Zhe,Dong, Zheng,Ma, Tong,Zhang, Yu,Zhao, Depeng,Zhao, Heng
, (2020/03/19)
We developed an efficient method for synthesis of substituted N-benzoylindole via Pd(II)-catalyzed C-H functionalization of substituted N-(2-allylphenyl)benzamide. The reaction showed a broad substrate scope (including N-acetyl and N-Ts substrates) and substituted indoles were obtained in good to excellent yields. The most distinctive feature of this method lies in the high selectivity for N-benzoylindole over benzoxazine, and this is the first example of Pd(II)-catalyzed synthesis of substituted N-benzoylindole. Notably, this new method was applied for the synthesis of key intermediate of indomethacin.
Lewis Base-Catalyzed Amino-Acylation of Arylallenes via C-N Bond Cleavage: Reaction Development and Mechanistic Studies
Xia, Ji-Bao,Yang, Yusheng,Yu, Zhi-Xiang,Zhang, Zheng-Bing
, p. 5419 - 5429 (2020/09/02)
Lewis base-catalyzed transformations of allenes have received much attention over the last decades. However, this type of reaction has so far been limited to activated allenes bearing an electron-withdrawing group. On the other hand, cleavage of an amide C-N bond to forge other chemical bonds has been widely reported but restricted to low atom economy due to the waste of the amine moiety of amides. We initiated a project of metal-catalyzed amino-acylation of allenes via cleavage of amide C-N bonds. Surprisingly, an amino-acylation of weakly activated aryl allenes was discovered via Lewis base catalysis, providing 2-methyl-3-aroylindole products, "privileged structures"in drug discovery. This is a unique example of Lewis base catalysis of weakly activated allenes, which was not reported yet. Extensive experimental and computational studies have been conducted to provide insight into the reaction mechanism. The nucleophilic addition of Lewis base catalyst to aryl allene is the rate-limiting step. A challenging [1,3]-proton transfer is realized by nitrogen anion intermediate assisted sequential [1,4]- and [1,6]-proton transfer in the reaction pathway.
Indole compound and synthesizing and application methods thereof
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, (2019/10/22)
The invention relates to an indole compound and synthesizing and application methods thereof. The indole compound is prepared by selecting specific substituent groups. Experiments find that the indolecompound can achieve good inhibiting effects on prostatic cancer, good in drug-resistance-proofness and low in side effects when applied as an anti-cancer drug; besides, the synthesizing method of the indole compound comprises subjecting a compound with the structure shown as the formula (II), palladium acetate, benzoquinones and organic acids to reaction in solvent to obtain the indole compoundwith the structure shown as the formula (I). Experiment results show that the synthesizing method of the indole compound is low in requirements on substrate and high in product yield.
Palladium-Catalyzed Carbonylative Dearomatization of Indoles
Wang, Hai,Wu, Xiao-Feng
supporting information, p. 5264 - 5268 (2019/07/03)
An interesting palladium-catalyzed dearomative carbonylation of N-(2-bromobenzoyl)indoles has been developed. The catalytic system is composed of commercially available Pd(OAc)2 and DPPP and uses alcohols and anilines as nucleophiles to afford moderate to good yields of the desired products. This method provides a straightforward access to diverse fused indoline esters and amides with good functional group tolerance. Remarkably, this is the first example of carbonylative dearomatization.
Water-Soluble Hypervalent Iodine(III) Having an I-N Bond. A Reagent for the Synthesis of Indoles
Xia, Hai-Dong,Zhang, Yan-Dong,Wang, Yan-Hui,Zhang, Chi
, p. 4052 - 4056 (2018/07/15)
A readily accessible and bench-stable water-soluble hypervalent iodine(III) reagent (phenyliodonio)sulfamate (PISA) with an I-N bond was synthesized, and its structure was characterized by X-ray crystallography. With PISA, various indoles were synthesized via C-H amination of 2-alkenylanilines involving an aryl migration/intramolecular cyclization cascade with excellent regioselectivity in aqueous CH3CN. Notably, using this new method as the key step, not only two drug molecules, indometacin and zidometacin, but also another bioactive molecule, pravadoline, were synthesized.
Fluorine as a Traceless Directing Group for the Regiodivergent Synthesis of Indoles and Tryptophans
Andries-Ulmer, Anna,Brunner, Christoph,Rehbein, Julia,Gulder, Tanja
supporting information, p. 13034 - 13041 (2018/09/27)
Despite ample evidence for the unique reactivity offered by hypervalent F-iodanes, mechanistic investigations fall far behind. In order to shed light on the unusual behavior of such F-reagents, we conducted computational and experimental studies on the chemodivergent transformation of styrenes. We identified the spirocyclic F-cyclopropane as the common intermediate for both the C,H-fluorination and C,H-amination pathways. The fate of this key compound is determined by the extent of cationic charge delocalization controlled by the N-substituents. Exploiting this phenomenon, a multitude of different transformations have become available, leading, i.e., to the regiodivergent synthesis of indoles and tryptophans.
Application of hypervalent iodine reagent-mediated in preparation of indole derivatives
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Paragraph 0061, (2018/11/22)
The invention relates to application of hypervalent iodine reagent-mediated in preparation of indole derivatives, in particular to the application of organic trivalent iodine reagent iodoyl benzene aminosulfonate in preparing N-protected 2-substituted indole compounds and indomethacin, zidometacin, pravadoline. The invention relates to the application of organic trivalent iodine reagent iodoyl benzene aminosulfonate in preparing N-protected 2-substituted indole compounds, and the reaction undergoes functional group exchange of a substrate. In addition, iodoyl benzene aminosulfonate plays two important roles in this application, as an oxidant and as Bronsted acid. The application has the advantages of good regioselectivity, wide substrate range, mild conditions, simple operation and amplification of experimental steps. The application of the organic trivalent iodine reagent iodoyl benzene aminosulfonate in the preparation of indomethacin, zidomeprin and pravadoline provided by the invention has the advantages of high synthesis efficiency, simple operation and the like.
C3-Selective alkenylation of N-acylindoles with unactivated internal alkynes by cooperative nickel/aluminium catalysis
Inoue, Fumiyoshi,Saito, Teruhiko,Semba, Kazuhiko,Nakao, Yoshiaki
supporting information, p. 4497 - 4500 (2017/04/26)
Highly regio- and stereoselective alkenylation of N-acylindoles with unactivated internal alkynes has been accomplished by cooperative nickel/aluminium catalysis to afford C3-alkenylated indoles. Coordination of the acyl moiety to a bulky aluminium-based Lewis acid plays a crucial role in the selective functionalization at the C3-position by electron-rich nickel(0) catalysis.
Preparation of magnetically recyclable MIL-53(Al)@SiO2@Fe3O4 catalysts and their catalytic performance for Friedel-Crafts acylation reaction
Jiang, Sai,Yan, Junlei,Habimana, Fabien,Ji, Shengfu
, p. 83 - 90 (2016/03/19)
Novel magnetically recyclable MIL-53(Al)@SiO2@Fe3O4 catalysts with different MIL-53(Al) contents were prepared by encapsulating magnetic SiO2@Fe3O4 nanoparticles into MIL-53(Al) through an in situ method. The structure of the catalysts was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, vibration sample magnetometer (VSM), and N2 adsorption/desorption techniques. Catalytic activity and recovery properties of the catalysts for Friedel-Crafts acylation reaction of 2-methylindole with benzoyl chloride were evaluated. The results showed that the magnetic MIL-53(Al)@SiO2@Fe3O4 catalysts have the larger surface areas, suitable superparamagnetism, and good catalytic activity for Friedel-Crafts acylation reaction. Over 38.8% MIL-53(Al)@SiO2@Fe3O4 catalyst under the reaction conditions of 25 °C for 8 h the conversion of 2-methylindole can reach ～98%, and the selectivity of 3-acetylindole and that of N-acetylindole can reach ～81% and ～18%, respectively. After the reaction, the catalyst can be easily separated from the reactant mixture by an external magnet. The recovered catalyst can be reused for five times, and the conversion of 2-methylindole can be kept over 90% and the selectivity of 3-acetylindole can be maintained at 80%.
