90395-45-2Relevant articles and documents
Biaryl Cross-Coupling Enabled by Photo-Induced Electron Transfer
Hayashi, Hirohito,Wang, Bin,Wu, Xiangyang,Teo, Shi Jie,Kaga, Atsushi,Watanabe, Kohei,Takita, Ryo,Yeow, Edwin K. L.,Chiba, Shunsuke
supporting information, p. 2223 - 2231 (2020/04/30)
We report a protocol for aryl cross-coupling of electron-deficient aryl halides with electron-rich (hetero)arenes that is driven solely by violet light. This process takes advantage of formation of photo-excited state of electron-deficient aryl halides, that are reduced by electron-rich (hetero)arenes to form a pair of aryl anion and cation radicals. The resulting aryl anion radicals of aryl halides undergo mesolysis of the carbon-halogen bond to generate aryl radicals, that are coupled most likely with aryl cation radicals to afford functionalized biaryls. (Figure presented.).
Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters
Fernández, Estefanía,Rivero-Crespo, Miguel A.,Domínguez, Irene,Rubio-Marqués, Paula,Oliver-Meseguer, Judit,Liu, Lichen,Cabrero-Antonino, María,Gavara, Rafael,Hernández-Garrido, Juan C.,Boronat, Mercedes,Leyva-Pérez, Antonio,Corma, Avelino
supporting information, p. 1928 - 1940 (2019/02/14)
The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling. With sub-nanometer Pd species, amines drive to the Heck reaction, carbonate drives to the Sonogahira reaction, and phosphate drives to the Suzuki reaction, while for Pt clusters and single atoms, good conversion is only achieved using acetate as a base. This base-controlled orthogonal reactivity with ligand-free catalysts opens new avenues in the design of cross-coupling reactions in organic synthesis.
Pyridine substituted dibenzyl pyrimidine compound, and organic electroluminescence element thereof
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Paragraph 0086-0088; 0096-0098, (2019/08/12)
The invention provides a pyridine substituted dibenzyl pyrimidine compound with a structure represented by formula I, and an organic electroluminescence element adopted with the pyridine substituted dibenzyl pyrimidine compound, wherein X1, A1, and n are
PYRIDINE-SUBSTITUTED DIPHENYLPYRIMIDINES COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICES USING THE SAME
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Page/Page column 17-18; 21, (2019/11/26)
一種具式(I)結構之經吡啶取代之二苯基嘧啶化合物及使用該化合物之有機電激發光元件，其中，X1、A1及n係如同說明書中之定義。 The present invention provides pyridine-substituted diphenylpyrimidines compounds of formula (I) and an organic electroluminescent device using the same:wherein X1, A1and n are as defined in t
Novel Insights into the Combination of Metal- and Biocatalysis: Cascade One-Pot Synthesis of Enantiomerically Pure Biaryl Alcohols in Deep Eutectic Solvents
Paris, Juraj,Ríos-Lombardía, Nicolás,Morís, Francisco,Gr?ger, Harald,González-Sabín, Javier
, p. 4417 - 4423 (2018/09/14)
One of the pioneering examples of chemoenzymatic cascades in water such as the palladium-catalysed Suzuki-cross coupling followed by an enzymatic reduction has been revisited by the employment of a medium containing Deep Eutectic Solvents (DESs) for the catalytic performance. Thus, the unique properties of these neoteric solvents enabled to reach high substrate concentration for the overall process. Moreover, both isolated enzymes and whole cells exhibited excellent activities which allowed to obtain a set of chiral biaryl alcohols in good yields and very high enantiomeric excess (>99 %).
Pyridine sulfinates as general nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions with aryl halides
Markovic, Tim,Rocke, Benjamin N.,Blakemore, David C.,Mascitti, Vincent,Willis, Michael C.
, p. 4437 - 4442 (2017/07/11)
Pyridine rings are ubiquitous in drug molecules; however, the pre-eminent reaction used to form carbon-carbon bonds in the pharmaceutical industry, the Suzuki-Miyaura cross-coupling reaction, often fails when applied to these structures. This phenomenon is most pronounced in 2-substituted pyridines, and results from the difficulty in preparing, the poor stability of, and low efficiency in reactions of pyridine-2-boronates. We demonstrate that by replacing these boronates with pyridine-2-sulfinates, a cross-coupling process of unrivalled scope and utility is realized. The corresponding 3-And 4-substituted pyridine variants are also efficient coupling partners. In addition, we apply these sulfinates in a library format to the preparation of medicinally relevant derivatives of the drugs varenicline (Chantix) and mepyramine (Anthisan).
Co/NHPI-mediated aerobic oxygenation of benzylic C-H bonds in pharmaceutically relevant molecules
Hruszkewycz, Damian P.,Miles, Kelsey C.,Thiel,Stahl, Shannon S.
, p. 1282 - 1287 (2017/02/10)
A simple cobalt(ii)/N-hydroxyphthalimide catalyst system has been identified for selective conversion of benzylic methylene groups in pharmaceutically relevant (hetero)arenes to the corresponding (hetero)aryl ketones. The radical reaction pathway tolerates electronically diverse benzylic C-H bonds, contrasting recent oxygenation reactions that are initiated by deprotonation of a benzylic C-H bond. The reactions proceed under practical reaction conditions (1 M substrate in BuOAc or EtOAc solvent, 12 h, 90-100 °C), and they tolerate common heterocycles, such as pyridines and imidazoles. A cobalt-free, electrochemical, NHPI-catalyzed oxygenation method overcomes challenges encountered with chelating substrates that inhibit the chemical reaction. The utility of the aerobic oxidation method is showcased in the multigram synthesis of a key intermediate towards a drug candidate (AMG 579) under process-relevant reaction conditions.
METHOD OF SYNTHESIS MOLECULES USING CATALYST AND COMPOSITES THEREOF
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Sheet 9/14, (2014/11/13)
A method to synthesis molecules is provided. The method employs a catalyst for a cross- coupling react ion to obtain the molecule. The method comprises coupling boronic acid and halide in presence of the catalyst having graphite oxide supported palladium nanoparticles, a solvent and a base by heating. The heating is performed at a temperature lower than the temperature at which the graphite oxide deforms. The molecule is a biaryl. The method further provides obtaining complexs such as boscalid, telmisartan, valsartan, and SPPARMγ.
Nickel-catalyzed one-pot Suzuki-Miyaura cross-coupling of phenols and arylboronic acids mediated by N,N-ditosylaniline
Chen, Liangshun,Lang, Hongyue,Fang, Lei,Zhu, Mengyun,Liu, Jinqian,Yu, Jianjun,Wang, Limin
supporting information, p. 4953 - 4957 (2014/08/18)
An efficient method for the construction of two distinct C aryl-Caryl bonds through the Ni-catalyzed Suzuki-Miyaura cross-coupling of phenols with arylboronic acids has been developed. This reaction proceeds through the in situ tosylation of phenols by using N,N-ditosylaniline as the sulfonylating reagent, which is highly active, markedly stable, and easily prepared. The scope with respect to the coupling partners - phenols and boronic acids - is broad, and sensitive functional groups are tolerated. Phenols, especially those containing an unprotected amino group, which are generally problematic for coupling under conventional one-pot conditions, are also viable substrates in this transformation.
Palladium nanoparticles on graphite oxide: A recyclable catalyst for the synthesis of biaryl cores
Santra, Subhankar,Hota, Pradip Kumar,Bhattacharyya, Rangeet,Bera, Parthasarathi,Ghosh, Prasenjit,Mandal, Swadhin K.
, p. 2776 - 2789 (2014/01/06)
The synthesis of life saving drug molecules in a cost-effective and environmentally benign pathway is of paramount significance. We present an environment friendly protocol to prepare core moieties of top selling drug molecules such as boscalid and telmisartan using Suzuki-Miyaura coupling conditions. In contrast to the traditional synthesis of these pharmaceutically important molecules, we have accomplished a graphite oxide (GO) supported palladium nanoparticles (PdNPs) based catalyst which quantitatively produced these core biaryl moieties of top selling drug molecules in a recyclable way. The catalytic activity remained unchanged even after 16 successive catalytic cycles without incorporating any palladium metal impurity in the pharmaceutically significant organic products. A detailed study including IR spectroscopy, solid state NMR spectroscopy, X-ray photoelectron spectroscopy, and DFT calculation was employed to understand the role of solid support on the nondecaying recycling ability of the catalyst during the Suzuki-Miyaura coupling reaction. The study indicates a strong chemical interaction of the different functionalities present in the GO, with the palladium centers which is primarily responsible for such sustained catalytic activity during the consecutive Suzuki-Miyaura coupling cycles.
