- Photocatalytic C–X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles
-
Hierarchical SiC nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C-X (X = Br, I) borylation of aryl halides at 30 °C. The SiC/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from SiC to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C-I or C-Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/SiC photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.
- Jiao, Zhi-Feng,Zhao, Ji-Xiao,Guo, Xiao-Ning,Guo, Xiang-Yun
-
-
Read Online
- Reactive Oxygen Species (ROS)-sensitive prodrugs of the tyrosine kinase inhibitor crizotinib
-
Tyrosine kinase inhibitors revolutionized cancer therapy but still evoke strong adverse effects that can dramatically reduce patients' quality of life. One possibility to enhance drug safety is the exploitation of prodrug strategies to selectively activate a drug inside the tumor tissue. In this study, we designed a prodrug strategy for the approved c-MET, ALK, and ROS1 tyrosine kinase inhibitor crizotinib. Therefore, a boronic-acid trigger moiety was attached to the 2-aminopyridine group of crizotinib, which is a crucial position for target kinase binding. The influence of the modifications on the c-MET- and ALK-binding ability was investigated by docking studies, and the strongly reduced interactions could be confirmed by cell-free kinase inhibition assay. Furthermore, the newly synthesized compounds were tested for their activation behavior with H2O2 and their stability in cell culture medium and serum. Finally, the biological activity of the prodrugs was investigated in three cancer cell lines and revealed a good correlation between activity and intrinsic H2O2 levels of the cells for prodrug A. Furthermore, the activity of this prodrug was distinctly reduced in a non-malignant, c-MET expressing human lung fibroblast (HLF) cell line.
- Ahmed, Esra,Bielec, Bjoern,Heffeter, Petra,Keppler, Bernhard K.,Kowol, Christian R.,Poetsch, Isabella
-
-
Read Online
- Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water
-
A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 h in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.
- Zernickel, Anna,Du, Weiyuan,Ghorpade, Seema A.,Sawant, Dinesh N.,Makki, Arwa A.,Sekar, Nagaiyan,Eppinger, J?rg
-
-
Read Online
- Discovery of phenyl-linked symmetric small molecules as inhibitors of the programmed cell death-1/programmed cell death-ligand 1 interaction
-
Programmed cell death-1/programmed cell death ligand 1 (PD-1/PD-L1) is one of the most promising targets in the field of immune checkpoint blockade therapy. Beginning with our exploration of linkers and structure-activity relationship research, we found that the aromatic ring could replace the linker and aryl group to maintain the satisfactory activity of classic triaryl scaffold inhibitor. Based on previous studies, we designed and synthesized a series of C2-symmetric phenyl-linked compounds, and further tail optimization afforded the inhibitors, which displayed promising inhibitory activity against the PD-1/PD-L1 interaction with IC50 value at the single nanomolar range (C13–C15). Further cell-based PD-1/PD-L1 blockade bioassays indicated that these C2-symmetric molecules could significantly inhibit the PD-1/PD-L1 interaction at the cellular level and restore T cells' immune function at the safety concentrations. The discovery of these phenyl-linked symmetric small molecules showed the potential of simplified-linker and C2-symmetric strategy and provided a basis for developing symmetric small molecule inhibitors of PD-1/PD-L1 interaction. Moreover, C13 and C15 performed stable binding modes to PD-L1 dimeric after computational docking and dynamic simulation, which may serve as a good starting point for further development.
- Wu, Yizhe,Zhang, Yu,Guo, Yu,Pan, Zhichao,Zhong, Shichun,Jin, Xinxin,Zhuang, Weihao,Chen, Sikang,Gao, Jian,Huang, Wenhai,Dong, Xiaowu,Che, Jinxin
-
-
Read Online
- Use of in situ isopropoxide protection in the metal-halogen exchange of arylboronates
-
(Chemical Equation Presented) Isopropoxide protection of arylboronates allowed their use in metal-halogen exchange reactions. The isopropoxide- protected borate species were obtained from a boronate or in situ from dibromoarenes. meta- and para-dibromoare
- Jiang, Qin,Ryan, Meagan,Zhichkin, Paul
-
-
Read Online
- Microwave-assisted synthesis of pinacol boronates from aryl chlorides catalyzed by a palladium/imidazolium salt system
-
(formula presented) Aryl chlorides bearing electron-withdrawing groups react with bis(pinacol)borane 1 to give aryl boronates in good to excellent yields in the presence of a catalyst formed in situ from Pd(OAc)2 and the imidazolium chloride 2. The reaction is greatly accelerated when carried out under microwave heating.
- Fuerstner, Alois,Seidel, Guenter
-
-
Read Online
- Behavior of Supramolecular Assemblies of Radiometal-Filled and Fluorescent Carbon Nanocapsules In?Vitro and In?Vivo
-
Hybrid materials based on supramolecularly assembled single-walled carbon nanotubes (SWNTs) are generated for positron emission tomography (PET), magnetic resonance imaging, and fluorescence imaging. The all-in-one imaging probe allows quantitative imaging from subcellular resolution to whole tissue regions. The SWNTs can be exposed to aqueous solutions of non-radioactive and radioactive metal salts in the presence of fullerenes and β-D-glucan. Encapsulating 64Cu ions achieves a minimum of 69% incorporation of radiochemical. The results suggest that this method can be extended to other metal ions of medical relevance, such as zirconium(IV)-89 or rhenium(VII)-188, which are used for medical imaging or radiotherapy, respectively. The in vivo uptake of 64Cu(II)@SWNT@β-D-glucan in Wistar rats allows the investigation of organ biodistribution by microPET. Radioactivity rapidly accumulates predominantly in the lungs and myocardium with peak uptakes of 4.8 ± 0.9 standardized uptake value. Furthermore, such materials are fully traceable in cells by multiphoton fluorescence lifetime imaging with near-infrared excitation (910 nm).
- Ge, Haobo,Riss, Patrick J.,Mirabello, Vincenzo,Calatayud, David G.,Flower, Stephen E.,Arrowsmith, Rory L.,Fryer, Tim D.,Hong, Young,Sawiak, Steve,Jacobs, Robert M.J.,Botchway, Stanley W.,Tyrrell, Rex M.,James, Tony D.,Fossey, John S.,Dilworth, Jonathan R.,Aigbirhio, Franklin I.,Pascu, Sofia I.
-
-
Read Online
- An improved procedure for the synthesis of arylboronates by palladium-catalyzed coupling reaction of aryl halides and bis(pinacolato)diboron in polyethylene glycol
-
A new protocol has been developed for the synthesis of arylboronates by a coupling reaction of aryl halides and bis(pinacolato)diboron using bis(triphenylphosphine)palladium dichloride/sodium acetate/polyethylene glycol 600 [Pd(PPh3)2Cl2/NaOAc/PEG 600] as an efficient catalytic system. Copyright
- Lu, Jie,Guan, Zhong-Zhi,Gao, Jian-Wu,Zhang, Zhan-Hui
-
-
Read Online
- Nitro-substituted stilbeneboronate pinacol esters and their fluoro-adducts. Fluoride ion induced polarity enhancement of arylboronate esters
-
(Chemical Equation Presented) A series of stilbeneboronate pinacol cyclic esters, containing none to three nitro groups, have been synthesized by various olefination reactions and characterized by X-ray single-crystal structure analysis. A stilbeneboronat
- Oehlke, Alexander,Auer, Alexander A.,Jahre, Ina,Walfort, Bernhard,Rueffer, Tobias,Zoufala, Petra,Lang, Heinrich,Spange, Stefan
-
-
Read Online
- One-pot preparation of unsymmetrical biaryls via Suzuki cross-coupling reaction of aryl halide using phase-transfer catalyst in a biphasic solvent system
-
A one-pot synthetic method of unsymmetrical biaryls was developed via the Suzuki cross-coupling reaction of aryl halide using a phase-transfer catalyst in a biphasic solvent system. Copyright Taylor & Francis Group, LLC.
- Miura, Masanori,Koike, Takanori,Ishihara, Tsukasa,Sakamoto, Shuichi,Okada, Minoru,Ohta, Mitsuaki,Tsukamoto, Shin-Ichi
-
-
Read Online
- Pd(II) Complexes with Chelating Phosphinoferrocene Diaminocarbene Ligands: Synthesis, Characterization, and Catalytic Use in Pd-Catalyzed Borylation of Aryl Bromides
-
We developed a novel, straightforward route toward Pd(II)-aminocarbene complexes bearing a P-chelating phosphinoferrocenyl substituent based on a three-component reaction of 1′-(diphenylphosphino)-1-isocyanoferrocene (1) with [PdCl2(cod)] (cod = cycloocta-1,5-diene) and nucleophilic amines. Depending on the type of the amine, the reaction produced acyclic diaminocarbenes and their saturated (imidazolin-2-ylidene) and unsaturated (imidazol-2-ylidene) cyclic counterparts (NHCs). Using (S)-2-(chloromethyl)pyrrolidine as the nucleophile, this method afforded a separable pair of stable diastereomeric bicyclic imidazolin-2-ylidene carbenes with different configurations of the planar-chiral ferrocene unit. The prepared P-chelating carbenes were characterized using spectroscopic methods, X-ray crystallography, and DFT methods. The last were used to explain the formation of isomeric open diaminocarbenes featuring NHR groups at the wing-tip position, trends in Pd-Cl bond lengths reflecting similar trans influences of the particular carbene and phosphine donors, and the results from cyclic voltammetric measurements. Furthermore, the carbenes were used as defined (pre)catalysts in Miyaura borylation of aryl bromides with bis(pinacolato)diboron. When applying the optimized catalytic system (1 mol % Pd catalyst, KOAc as the base, 2-propanol, 85 °C), this reaction produced a range of simple and substituted arylboronate pinacol esters in high yield and without biaryl side products.
- ?koch, Karel,Schulz, Ji?í,Císa?ová, Ivana,?těpni?ka, Petr
-
-
Read Online
- Redox-Neutral Decarbonylative Cross-Couplings Coming of Age
-
Major progress has recently been made in the challenging redox-neutral decarbonylative cross-coupling of carboxylic acids. For example, the use of acid fluorides as effective cross-coupling partners has been found to enable control of the decarbonylation selectivity and facilitates challenging Pd0-catalyzed nucleophilic trifluoromethylation and exogenous base-free Suzuki cross-coupling reactions. In another recent advance, the use of acid chlorides in room temperature difluoromethylation and direct decarbonylative cross-coupling of carboxylic acids allows these classical substrates to be used as aryl electrophiles in cross-coupling reactions. Further challenges that are yet to be addressed in redox-neutral decarbonylative cross-couplings are also briefly summarized.
- Zhao, Qun,Szostak, Michal
-
-
Read Online
- Isophorone-boronate ester: A simple chemosensor for optical detection of fluoride anion
-
A highly selective isophorone-boronate ester based chemosensor, (1), having a dicyanovinyl moiety as a convenient colorimetric probe, has been designed. Different types of anionic analyte such as CH3COO?, ClO4?,
- Ranjith Kumar, Jakku,Rami Reddy, Eda,Trivedi, Rajiv,Vardhaman, Anil Kumar,Giribabu, Lingamallu,Mirzadeh, Nedaossadat,Bhargava, Suresh K.
-
-
Read Online
- Synthesis of pinacol arylboronates via cross-coupling reaction of bis(pinacolato)diboron with chloroarenes catalyzed by palladium(0)-tricyclohexylphosphine complexes
-
The cross-coupling reaction of bis(pinacolato)diboron with chloroarenes to yield pinacol arylboronates was carried out in 1,4-dioxane at 80°C in the presence of KOAc (1.5 equiv.) and Pd(dba)2/2.4PCy3 (3-6 mol%). The catalyst was also effective to carry out analogous coupling with aryl bromides or triflates under milder conditions than those of the previous procedures catalyzed by PdCl2(dppf) in DMSO.
- Ishiyama, Tatsuo,Ishida, Kousaku,Miyaura, Norio
-
-
Read Online
- 1-[5-(4,5-Dimethyl-1,3,2-dioxaboro-lan-2-yl)thio-phen-2-yl]ethanone and 4-(4,4,5,5-tetra-methyl-1,3,2-dioxa-borolan-2-yl)benzaldehyde
-
In both title compounds, C10H13BO3S, (I), and C13H17BO3, (II), the mol-ecules adopt nearly planar conformations. The crystal packing of (I) consists of a supra-molecular two-dimensional network with a herringbone-like topology formed by self assembly of centrosymmetric pairs of mol-ecules linked via dipole-dipole inter-actions. The crystal structure of (II) consists of a supra-molecular two-dimensional network built up from centrosymmetric pairs of mol-ecules via π-π inter-actions. These pairs of mol-ecules are self-organized in an offset fashion related by a symmetry centre, generating supra-molecular ribbons running along the [101] direction. Neighbouring ribbons are stacked via complementary van der Waals and hydro-phobic methyl-methyl inter-actions.
- Urdaneta, Neudo,Nuez, Jess,Gonzalez, Teresa,Briceo, Alexander
-
-
Read Online
- Synthesis of some para-functionalized phenylboronic acid derivatives
-
Straightforward preparations of para-, carboxy-, hydroxymethyl- and bromo methyl phenylboronic acid derivatives from para-formyl-phenylboronic acid as a common precursor are presented.
- De Filippis, Arnault,Morin, Christophe,Thimon, Christian
-
-
Read Online
- Facile and economical Miyaura borylation and one-pot Suzuki–Miyaura cross-coupling reaction
-
Facile and economical method for Miyaura borylation reaction between B2pin2 and aryl bromides is reported. The catalytic system containing 2 mol% PdCl2(PPh3)2 and KOAc serves to enable borylations to occur under solvent-free and atmospheric conditions. The developed protocol can be applied to synthesize symmetrical and unsymmetrical biaryls via one-pot two-step Suzuki–Miyaura cross-coupling reaction and also offers the up-scalability.
- Boontiem, Phongsakorn,Kiatisevi, Supavadee
-
-
Read Online
- Oxidation of alcohols to aldehydes with bromoisobutyrate and dimethyl sulfoxide
-
We have developed an efficient oxidation of primary alcohols to aldehydes with ethyl bromoisobutyrate and dimethyl sulfoxide. Diaryl ketone can also be prepared under this reaction system.
- Wu, Fei-Yue,Chen, Xiao-Hui,Zhou, Hai-Mei,Li, Jia-Qin,Cui, Hai-Lei
-
supporting information
(2021/09/29)
-
- Metal- And additive-free C-H oxygenation of alkylarenes by visible-light photoredox catalysis
-
A metal- and additive-free methodology for the highly selective, photocatalyzed C-H oxygenation of alkylarenes under air to the corresponding carbonyls is presented. The process is catalyzed by an imide-acridinium that forms an extremely strong photooxidant upon visible light irradiation, which is able to activate inert alkylarenes such as toluene. Hence, this is an easy to perform, sustainable and environmentally friendly oxidation that provides valuable carbonyls from abundant, readily available compounds.
- García Manche?o, Olga,Kuhlmann, Jan H.,Pérez-Aguilar, María Carmen,Piekarski, Dariusz G.,Uygur, Mustafa
-
supporting information
p. 3392 - 3399
(2021/05/21)
-
- Anodic Oxidation of Aminotetrazoles: A Mild and Safe Route to Isocyanides
-
A new electrochemical method for the preparation of isocyanides from easily accessible aminotetrazole derivatives has been developed, which tolerates an unprecedented range of functional groups. The use of chemical, rather than electrochemical, oxidation to afford isocyanides was also demonstrated, which provides access to these compounds for those without electrosynthesis equipment. The practicality of scale-up using flow electrochemistry has been demonstrated, in addition to the possibility of using electrochemically generated isocyanides in further reactions.
- Leech, Matthew C.,Petti, Alessia,Tanbouza, Nour,Mastrodonato, Andrea,Goodall, Iain C. A.,Ollevier, Thierry,Dobbs, Adrian P.,Lam, Kevin
-
supporting information
p. 9371 - 9375
(2021/12/09)
-
- Nickel-Mediated Enantiospecific Silylation via Benzylic C-OMe Bond Cleavage
-
Benzylic stereocenters are found in bioactive and drug molecules, as enantiopure benzylic alcohols have been used to build such a stereogenic center, but are limited to the construction of a C-C bond. Silylation of alkyl alcohols has the potential to build bioactive molecules and building blocks; however, the development of such a process is challenging and unknown. Herein, we describe an unprecedented AgF-assisted nickel catalysis in the enantiospecific silylation of benzylic ethers.
- Balakrishnan, Venkadesh,Murugesan, Vetrivelan,Chindan, Bincy,Rasappan, Ramesh
-
supporting information
p. 1333 - 1338
(2021/02/20)
-
- Synthesis and luminescence properties of two cross-linkable Ir(iii) complexes
-
Two cross-linkable iridium(iii) complexes, Ir(L)2(acac) and Ir(L)2(Stpip), where L = 1-phenyl-2-(4′-vinyl-[1,1′-biphenyl]-4-yl)-1H-benzo[d]imidazole, acac = acetylacetonate, and Stpip = bis(diphenylphorothioyl)amide, were synthesized
- Li, Yanmei,Liu, Xiaoxiao,Su, Wenming,Wang, Ruidong,Wang, Youjia,Wu, Shaoguang,Yu, Tianzhi,Zhang, Di,Zhao, Yuling
-
p. 19154 - 19163
(2021/10/29)
-
- Recyclable Pd2dba3/XPhos/PEG-2000 System for Efficient Borylation of Aryl Chlorides: Practical Access to Aryl Boronates
-
Pd2dba3/XPhos in poly(ethylene glycol) (PEG-2000) is shown to be a highly stable and efficient catalyst for the borylation of aryl chlorides with bis(pinacolato)diboron. The borylation reaction proceeds smoothly at 110 °C, delivering a wide variety of aryl boronates in good to excellent yields with high functional group tolerance. The crude products were easily isolated via simple extraction of the reaction mixture with cyclohexane. Moreover, both expensive Pd2dba3 and XPhos in PEG-2000 system could be readily recycled and reused more than six times without loss of catalytic efficiency.
- Cai, Mingzhong,Huang, Bin,Luo, Chengkai,Xu, Caifeng
-
-
- Electrochromic properties of pyrene conductive polymers modified by chemical polymerization
-
Pyrene is composed of four benzene rings and has a unique planar melting ring structure. Pyrene is the smallest condensed polycyclic aromatic hydrocarbon, and its unique structural properties have been extensively studied. Pyrene has excellent properties such as thermal stability, high fluorescence quantum efficiency and high carrier mobility. This paper mainly used thiophene, EDOT and triphenylamine groups to enhance the pyrene based π-conjugated system and control the molecular accumulation of organic semiconductors, and improve their charge transport performances. Five kinds of polymer were synthesized and correspondingly characterized. The five kinds of pyrene conductive polymer had outstanding properties in terms of solubility, fluorescence intensity and thermal stability, good film-forming properties, stable electrochromic properties and high coloring efficiency. The coloration efficiency (CE) of PPYTP was as high as 277 cm2C?1, and the switching response time was short. The coloring time of PPYEDOT was 1.3 s and the bleaching time was 3.2 s. The lower impedance will also provide the possibility of such polymers being incorporated into electrochromic devices in the future. In short, the synthesized new pyrene conductive polymers will have wide application prospects in the field of electrochromic materials.
- Chang, Lijing,Hou, Yanjun,Li, Rui,Ma, Yang,Miao, Shoulei,Wang, Cheng,Xu, Haoran,Zhang, Yuhang
-
p. 39291 - 39305
(2021/12/27)
-
- Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones
-
Direct conversion of aldehydes and ketones into alkylboronic esters via deoxygenative borylation represents an unknown yet highly desirable transformation. Herein, we present a one-step and metal-free method for carbonyl deoxy-borylation under mild conditions. A wide range of aromatic aldehydes and ketones are tolerated and successfully converted into the corresponding benzylboronates. By the same deoxygenation manifold with aliphatic aldehydes and ketones, we also enable a concise synthesis of 1,1,2-tris(boronates), a family of compounds that currently lack efficient synthetic methods. Given its simplicity and versatility, we expect that this novel borylation approach could show great promise in organoboron synthesis and inspire more carbonyl deoxygenative transformations in both academic and industrial settings.
- Huang, Chia-Yu,Li, Chao-Jun,Li, Jianbin,Qiu, Zihang,Wang, Haining
-
supporting information
p. 13011 - 13020
(2020/09/01)
-
- Sequential Connection of Mutually Exclusive Catalytic Reactions by a Method Controlling the Presence of an MOF Catalyst: One-Pot Oxidation of Alcohols to Carboxylic Acids
-
A functionalized metal-organic framework (MOF) catalyst applied to the sequential one-pot oxidation of alcohols to carboxylic acids controls the presence of a heterogeneous catalyst. The conversion of alcohols to aldehydes was acquired through aerobic oxidation using a well-known amino-oxy radical-functionalized MOF. In the same flask, a simple filtration of the radical MOF with mild heating of the solution completely altered the reaction media, providing radical scavenger-free conditions suitable for the autoxidation of the aldehydes formed in the first step to carboxylic acids. The mutually exclusive radical-catalyzed aerobic oxidation (the first step with MOF) and radical-inhibited autoxidation (the second step without MOF) are sequentially achieved in a one-pot manner. Overall, we demonstrate a powerful and efficient method for the sequential oxidation of alcohols to carboxylic acids by employing a readily functionalizable heterogeneous MOF. In addition, our MOF in-and-out method can be utilized in an environmentally friendly way for the oxidation of alcohols to carboxylic acids of industrial and economic value with broad functional group tolerance, including 2,5-furandicarboxylic acid and 1,4-benzenedicarboxylic acid, with good yield and reusability. Furthermore, MOF-TEMPO, as an antioxidative stabilizer, prevents the undesired oxidation of aldehydes, and the perfect "recoverability"of such a reactive MOF requires a re-evaluation of the advantages of MOFs from heterogeneity in catalytic and related applications.
- Kim, Seongwoo,Lee, Ha-Eun,Suh, Jong-Min,Lim, Mi Hee,Kim, Min
-
supporting information
p. 17573 - 17582
(2020/12/22)
-
- Visible Light-Induced Borylation of C-O, C-N, and C-X Bonds
-
Boronic acids are centrally important functional motifs and synthetic precursors. Visible light-induced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C-O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron-rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reaction exhibits excellent functional group tolerance, as demonstrated by the borylation of a range of structurally complex substrates. Remarkably, the reaction is catalyzed by phenothiazine, a simple organic photocatalyst with MW 200 that mediates the previously unachievable visible light-induced single electron reduction of phenol derivatives with reduction potentials as negative as approximately - 3 V versus SCE by a proton-coupled electron transfer mechanism. Mechanistic studies point to the crucial role of the photocatalyst-base interaction.
- Arman, Hadi D.,Dang, Hang. T.,Haug, Graham C.,He, Ru,Jin, Shengfei,Larionov, Oleg V.,Nguyen, Viet D.,Nguyen, Vu T.,Schanze, Kirk S.
-
supporting information
(2020/02/04)
-
- IMMUNOMODULATORS, COMPOSITIONS AND METHODS THEREOF
-
Provided herein are compounds of Formula (I), methods of using the compounds as immunomodulators, and pharmaceutical compositions comprising such compounds. The compounds are useful in treating, preventing or ameliorating diseases or disorders such as cancer or infections.
- -
-
Page/Page column 98
(2020/08/22)
-
- Copolymers for iodide detection and methods thereof
-
Copolymers having thiophene based and vinylene based moieties. Methods of producing the copolymers, and methods of utilizing the copolymers as chromogenic sensors for selective detection of iodide anion are also provided.
- -
-
-
- Indole hydrogen peroxide fluorescent probe and preparation method thereof
-
The invention provides an indole hydrogen peroxide fluorescent probe and a preparation method thereof, and belongs to the field of organic dye synthesis. The indole hydrogen peroxide probe prepared bythe method is a black solid in appearance, and the melting point is within the range of 180-300 DEG C. The fluorescent probe has the advantages of novel structure, high sensitivity, good selectivity,high molar extinction coefficient, good light stability and the like; besides, the fluorescence emission wavelength of the hydrogen peroxide probe is 500-650 nm, biological background fluorescence interference can be effectively avoided, the hydrogen peroxide probe has excellent penetrability to the environment and biological tissues, and a sensitive tool is provided for detection and research oforganisms and trace hydrogen peroxide in the environment.
- -
-
Page/Page column 5-7
(2020/09/23)
-
- Quinoline hydrogen peroxide fluorescent probe and preparation method thereof
-
The invention provides a quinoline hydrogen peroxide fluorescent probe and a preparation method thereof, and belongs to the field of organic dye synthesis. The quinoline hydrogen peroxide probe prepared by the method is a black solid in appearance, and th
- -
-
Paragraph 0034; 0037; 0038; 0041; 0044; 0045; 0048; 0051
(2020/10/04)
-
- Benzoindole hydrogen peroxide fluorescent probe and preparation method thereof
-
The embodiment of the invention relates to the technical field of biological fluorescent probes, in particular to a benzoindole hydrogen peroxide fluorescent probe and a preparation method thereof. According to the benzoindole hydrogen peroxide fluorescent probe provided by the embodiment of the invention, phenylboronic acid pinacol ester is introduced, a specific hydrogen peroxide fluorescent probe with a novel structure is designed and synthesized by utilizing a reaction mechanism that hydrogen peroxide easily oxidizes phenylboronic acid pinacol ester into phenol, and the benzoindole hydrogen peroxide fluorescent probe is good in hydrogen peroxide selectivity, high in fluorescence quantum yield, high in sensitivity and molar extinction coefficient, and good in light stability. The preparation method of the benzoindole hydrogen peroxide fluorescent probe provided by the invention is simple in process, mild in condition, high in yield and low in cost.
- -
-
Paragraph 0048; 0050; 0056; 0058; 0062; 0064; 0068; 0070
(2021/01/15)
-
- Room temperature Pd(0)/Ad3P-catalyzed coupling reactions of aryl chlorides with bis(pinacolato)diboron
-
Room temperature Pd(0)/Ad3P-catalyzed cross-coupling reactions of aryl chlorides with bis(pinacolato)diboron are described. The Pd(0)/Ad3P catalyst, generated from Ad3P-coordinated acetanilide-based palladacycle complex, proved to be an efficient catalyst system for the Miyaura borylation reactions of a variety of aryl chlorides with bis(pinacolato)diboron. The mild reaction condition, the easy availability of the catalyst and good coupling yields make these reactions potentially useful in organic synthesis.
- Dong, Jie,Guo, Hui,Peng, Wei,Hu, Qiao-Sheng
-
supporting information
p. 760 - 763
(2019/02/16)
-
- Hydrogenation of (Hetero)aryl Boronate Esters with a Cyclic (Alkyl)(amino)carbene–Rhodium Complex: Direct Access to cis-Substituted Borylated Cycloalkanes and Saturated Heterocycles
-
We herein report the hydrogenation of substituted aryl- and heteroaryl boronate esters for the selective synthesis of cis-substituted borylated cycloalkanes and saturated heterocycles. A cyclic (alkyl)(amino)carbene-ligated rhodium complex with two dimethyl groups at the ortho-alkyl scaffold of the carbene showed high reactivity in promoting the hydrogenation, thereby enabling the hydrogenation of (hetero)arenes with retention of the synthetically valuable boronate group. This process constitutes a clean, atom-economic, as well as chemo- and stereoselective route for the generation of cis-configured, diversely substituted borylated cycloalkanes and saturated heterocycles that are usually elusive and difficult to prepare.
- Ling, Liang,He, Yuan,Zhang, Xue,Luo, Meiming,Zeng, Xiaoming
-
supporting information
p. 6554 - 6558
(2019/04/17)
-
- Palladium-Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation
-
Decarbonylative borylation of carboxylic acids is reported. Carbon electrophiles are generated directly after reagent-enabled decarbonylation of the in situ accessible sterically-hindered acyl derivative of a carboxylic acid under catalyst controlled conditions. The scope and the potential impact of this method are demonstrated in the selective borylation of a variety of aromatics (>50 examples). This strategy was used in the late-stage derivatization of pharmaceuticals and natural products. Computations reveal the mechanistic details of the unprecedented C?O bond activation of carboxylic acids. By circumventing the challenging decarboxylation, this strategy provides a general synthetic platform to access arylpalladium species for a wide array of bond formations from abundant carboxylic acids. The study shows a powerful combination of experiment and computation to predict decarbonylation selectivity.
- Liu, Chengwei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
-
supporting information
p. 16721 - 16726
(2018/11/30)
-
- MUSCARINIC M1 RECEPTOR POSITIVE ALLOSTERIC MODULATORS
-
The present invention relates to compounds of formula (I), or their isotopic forms, stereoisomers, tautomers or pharmaceutically acceptable salt (s) thereof as muscarinic M1 receptor positive allosteric modulators (M1 PAMs). The present invention describes the preparation, pharmaceutical composition and the use of compound formula (I).
- -
-
Page/Page column 51
(2018/03/25)
-
- PD-1/PD-L1 INHIBITORS
-
Compounds according to formula (I), methods of using said compounds singly or in combination with additional agents and compositions of said compounds for the treatment of cancer are disclosed.
- -
-
Page/Page column 493; 494
(2018/11/22)
-
- Room-temperature borylation and one-pot two-step borylation/Suzuki-Miyaura cross-coupling reaction of aryl chlorides
-
A highly efficient room-temperature borylation strategy of aryl chlorides is described. Utilizing Buchwald's second-generation preformed catalyst, boronate esters were obtained for a wide range of substrates in high yield. The method was also applied to Suzuki-Miyaura cross-coupling reaction in a one-pot two-step sequential manner, providing a facile and convenient access to the direct synthesis of biaryl compounds from aryl chlorides.
- Ji, Hong,Wu, Li-Yang,Cai, Jiang-Hong,Li, Guo-Rong,Gan, Na-Na,Wang, Zhao-Hua
-
p. 13643 - 13648
(2018/04/24)
-
- A visible-near-infrared fluorescent probe for peroxynitrite with large pseudo-Stokes and emission shift: Via through-bond energy and charge transfers controlled by energy matching
-
We reported a visible-near-infrared fluorescent probe for peroxynitrite detection with large pseudo-Stokes and emission shifts, based on through-bond energy transfer (TBET) in combination with intramolecular charge transfer (ICT). Pyrene was chosen as a fluorophore (acceptor), which has monomer/excimer fluorescence characteristics. A conjugated 1,2-dimethylenehydrazine structure was a linker and phenyl boronate was selected as a reaction site (donor) to design the probe (Py-PhB) using the chemical transformation from boronate to phenol, which results in the increase of the energy of the donor to match the energy of the acceptor and simultaneously achieves TBET and ICT between the donor (phenolate) and the acceptor (pyrene), leading to a fluorescence 'OFF-ON' in a red-shifted region and a large emission shift. The results show that the probe exhibits high selectivity to ONOO- with a detection limit of 3.54 μM. Favorable ICT from phenolate to pyrene makes the probe possess a large monomer emission shift (183 nm), red-shifted to organe-red light (598 nm). TBET ensures the probe with a large pseudo-Stokes shift of 244 nm. Furthermore, its excimer emits a near-infrared light (720 nm), which is extremely beneficial for bioimaging. In short, this probe offers a novel design strategy for designing the TBET fluorescent sensors emitting red or NIR light with large pseudo-Stokes and emission shifts.
- Guo, Yuxin,Lu, Gonghao,Zhuo, Jiezhen,Wang, Jiayu,Li, Xue,Zhang, Zhiqiang
-
p. 2489 - 2496
(2018/05/04)
-
- Ping-Pong Energy Transfer in a Boron Dipyrromethane Containing Pt(II)-Schiff Base Complex: Synthesis, Photophysical Studies, and Anti-Stokes Shift Increase in Triplet-Triplet Annihilation Upconversion
-
A boron dipyrromethane (BDP)-containing Pt(II)-Schiff base complex (Pt-BDP), showing ping-pong singlet-triplet energy transfer, was synthesized, and the detailed photophysical properties were investigated using various steady-state and time-resolved transient spectroscopies. Femtosecond/nanosecond transient absorption spectroscopies demonstrated that, upon selective excitation of the BDP unit in Pt-BDP at 490 nm, F?rster resonance energy transfer from the BDP unit to the Pt(II) coordination center occurred (6.7 ps), accompanied by an ultrafast intersystem crossing at the Pt(II) coordination center (1 ps) and triplet-triplet energy transfer back to the BDP moiety (148 ps). These processes generated a triplet state localized at BDP, and the lifetime was 103.2 μs, much longer than the triplet-state lifetime of Pt-Ph (3.5 μs), a complex without the BDP moiety. Finally, Pt-BDP was used as a triplet photosensitizer for triplet-triplet annihilation (TTA) upconversion through selective excitation of the BDP unit or the Pt(II) coordination center at lower excitation energy. An upconversion quantum yield of up to 10% was observed with selective excitation of the BDP moiety, and a large anti-Stokes shift of 0.65 eV was observed upon excitation of the lower-energy band of the Pt(II) coordination center. We propose that using triplet photosensitizers with the ping-pong energy-transfer process may become a useful method for increasing the anti-Stokes shift of TTA upconversion.
- Razi, Syed S.,Koo, Yun Hee,Kim, Woojae,Yang, Wenbo,Wang, Zhijia,Gobeze, Habtom,D'Souza, Francis,Zhao, Jianzhang,Kim, Dongho
-
supporting information
p. 4877 - 4890
(2018/05/22)
-
- Triplet Excited State of BODIPY Accessed by Charge Recombination and Its Application in Triplet-Triplet Annihilation Upconversion
-
The triplet excited state properties of two BODIPY phenothiazine dyads (BDP-1 and BDP-2) with different lengths of linker and orientations of the components were studied. The triplet state formation of BODIPY chromophore was achieved via photoinduced electron transfer (PET) and charge recombination (CR). BDP-1 has a longer linker between the phenothiazine and the BODIPY chromophore than BDP-2. Moreover, the two chromophores in BDP-2 assume a more orthogonal geometry both at the ground and in the first excited state (87°) than that of BDP-1 (34-40°). The fluorescence of the BODIPY moiety was significantly quenched in the dyads. The charge separation (CS) and CR dynamics of the dyads were studied with femtosecond transient absorption spectroscopy (kCS = 2.2 × 1011 s-1 and 2 × 1012 s-1 for BDP-1 and BDP-2, respectively; kCR = 4.5 × 1010 and 1.5 × 1011 s-1 for BDP-1 and BDP-2, respectively; in acetonitrile). Formation of the triplet excited state of the BODIPY moiety was observed for both dyads upon photoexcitation, and the triplet state quantum yield depends on both the linker length and the orientation of the chromophores. Triplet state quantum yields are 13.4 and 97.5% and lifetimes are 13 and 116 μs for BDP-1 and BDP-2, respectively. The spin-orbit charge transfer (SO-CT) mechanism is proposed to be responsible for the efficient triplet state formation. The dyads were used for triplet-triplet annihilation (TTA) upconversion, showing an upconversion quantum yield up to 3.2%.
- Chen, Kepeng,Yang, Wenbo,Wang, Zhijia,Iagatti, Alessandro,Bussotti, Laura,Foggi, Paolo,Ji, Wei,Zhao, Jianzhang,Di Donato, Mariangela
-
p. 7550 - 7564
(2017/10/19)
-
- Formal Ir-Catalyzed Ligand-Enabled Ortho and Meta Borylation of Aromatic Aldehydes via in Situ-Generated Imines
-
The ligand-enabled development of ortho and meta C-H borylation of aromatic aldehydes is reported. It was envisaged that while ortho borylation could be achieved using tert-butylamine as the traceless protecting/directing group, meta borylation proceeds via an electrostatic interaction and a secondary interaction between the ligand of the catalyst and the substrate. These ligand-substrate electrostatic interactions and secondary B-N interactions provide an unprecedented controlling factor for meta-selective C-H activation/borylation.
- Bisht, Ranjana,Chattopadhyay, Buddhadeb
-
supporting information
p. 84 - 87
(2016/01/25)
-
- Miyaura Borylation and One-Pot Two-Step Homocoupling of Aryl Chlorides and Bromides under Solvent-Free Conditions
-
Solvent-free protocols for Miyaura borylation and the one-pot, two-step homocoupling of aryl halides are reported for the first time. Bis(dibenzylideneacetone)palladium(0) [Pd(dba)2] is an optimal source of palladium for Miyaura borylation, while for one-pot two-step homocoupling palladium(II) acetate [Pd(OAc)2] gives highest yields. Aryl bromides are coupled most efficiently using the DPEphos ligand. Chlorides are coupled using XPhos. The developed protocols are robust, versatile and easily reproducible on a large scale.
- Dzhevakov, Pavel B.,Topchiy, Maxim A.,Zharkova, Daria A.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
-
p. 977 - 983
(2016/04/05)
-
- Visible-Light Photoredox Borylation of Aryl Halides and Subsequent Aerobic Oxidative Hydroxylation
-
Efficient and practical visible-light photoredox borylation of aryl halides and subsequent aerobic oxidative hydroxylation were developed. The protocols use readily available aryl halides and bis(pinacolato)diboron as the starting materials, fac-Ir(ppy)3 as the photocatalyst, and corresponding arylboronic esters and phenols were obtained in good yields. The methods show some advantages including simple equipment, mild conditions, easy operation, and wide substrate scope. Therefore, they should provide a valuable strategy for chemical transformations.
- Jiang, Min,Yang, Haijun,Fu, Hua
-
supporting information
p. 5248 - 5251
(2016/11/02)
-
- Diethyl boronobenzylphosphonates as substrates in Petasis reactions
-
The Petasis reaction of α-(N-benzylamino)boronobenzylphosphonates with amines and salicylaldehyde or glyoxalic acid gives the desired products in moderate to good yields. The efficiency of the reaction is strongly dependent on the structure of the amine.
- Rydzewska, Agata,Olender, Anna,Mucha, Artur,Kafarski, Pawe?
-
p. 107 - 117
(2017/02/19)
-
- DiiodoBodipy-perylenebisimide dyad/triad: Preparation and study of the intramolecular and intermolecular electron/energy transfer
-
2,6-diiodoBodipy-perylenebisimide (PBI) dyad and triad were prepared, with the iodoBodipy moiety as the singlet/triplet energy donor and the PBI moiety as the singlet/triplet energy acceptor. IodoBodipy undergoes intersystem crossing (ISC), but PBI is dev
- Mahmood, Zafar,Xu, Kejing,Kü?ük?z, Betül,Cui, Xiaoneng,Zhao, Jianzhang,Wang, Zhijia,Karatay, Ahmet,Yaglioglu, Halime Gul,Hayvali, Mustafa,Elmali, Ayhan
-
p. 3036 - 3049
(2015/03/30)
-
- Palladium-Catalyzed Monofluoromethylation of Arylboronic Esters with Fluoromethyl Iodide
-
The first palladium-catalyzed direct monofluoromethylation of arylboronic esters to produce monofluoromethyl arenes is reported. The reaction is typically carried out at room temperature within 4 h and has a good functional group tolerance. The monofluoromethylating agent, CH2FI, was readily prepared via a halogen-exchange process.
- Hu, Jingyu,Gao, Bing,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
-
supporting information
p. 3086 - 3089
(2015/06/30)
-
- Investigation of a lithium-halogen exchange flow process for the preparation of boronates by using a cryo-flow reactor
-
Conducting low-temperature organometallic reactions under continuous flow conditions offers the potential to more accurately control exotherms and thus provide more reproducible and scalable processes. Herein, progress towards this goal with regards to the lithium-halogen exchange/borylation reaction is reported. In addition to improving the scope of substrates available on a research scale, methods to improve reaction profiles and expedite purification of the products are also described. On moving to a continuous system, thermocouple measurements have been used to track exotherms and provide a level of safety for continuous processing of organometallic reagents. The use of an in-line continuous liquid-liquid separation device to circumvent labour intensive downstream off-line processing is also reported. A cool setup: A small footprint, modular setup based around a cryo-flow reactor is reported for the preparation of gram quantities of boronic esters. With minimum alteration, including the addition of a data logger with thermocouples and a liquid-liquid separator, the same equipment can be used to scale the process, inclusive of an in-line extraction. Copyright
- Newby, James A.,Huck, Lena,Blaylock, D. Wayne,Witt, Paul M.,Ley, Steven V.,Browne, Duncan L.
-
p. 263 - 271
(2014/01/17)
-
- 2-AMINOPYRAZINE DERIVATIVES AS CSF-1 R KINASE INHIBITORS
-
The present invention provides a compound of formula (I) or a pharmaceutically acceptable salt, N-oxide, hydrate or solvate thereof: wherein:ring A, R1, R2, n, X, V, W, Z, ring B, [Linker] and R areas defined herein. The compounds are useful as inhibitorsof CSF-1R kinase. The compounds can thus be used in medicine.
- -
-
Page/Page column 39; 40
(2014/01/17)
-
- Synthesis of pinacol arylboronates from aromatic amines: A metal-free transformation
-
A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.
- Qiu, Di,Jin, Liang,Zheng, Zhitong,Meng, He,Mo, Fanyang,Wang, Xi,Zhang, Yan,Wang, Jianbo
-
p. 1923 - 1933
(2013/03/29)
-
- ANTIBACTERIAL AGENTS
-
Antibacterial compounds of formula (I) are provided, as well as stereoisomers and pharmaceutically acceptable salts thereof; pharmaceutical compositions comprising such compounds; methods of treating bacterial infections by the administration of such compounds; and processes for the preparation of such compounds.
- -
-
Page/Page column 93
(2013/12/03)
-
- Copper-mediated fluorination of arylboronate esters. Identification of a Copper(III) fluoride complex
-
A method for the direct conversion of arylboronate esters to aryl fluorides under mild conditions with readily available reagents is reported. Tandem reactions have also been developed for the fluorination of arenes and aryl bromides through arylboronate ester intermediates. Mechanistic studies suggest that this fluorination reaction occurs through facile oxidation of Cu(I) to Cu(III), followed by rate-limiting transmetalation of a bound arylboronate to Cu(III). Fast C-F reductive elimination is proposed to occur from an aryl-copper(III)-fluoride complex. Cu(III) intermediates have been generated independently and identified by NMR spectroscopy and ESI-MS.
- Fier, Patrick S.,Luo, Jingwei,Hartwig, John F.
-
supporting information
p. 2552 - 2559
(2013/03/29)
-
- Synthesis of amines with pendant boronic esters by borrowing hydrogen catalysis
-
Amine alkylation reactions of alcohols have been performed in the presence of boronic ester groups to provide products which are known to have use as molecular sensors. The boronic ester moiety could be present in either the alcohol or amine starting mate
- Ma, Winson M. J.,James, Tony D.,Williams, Jonathan M. J.
-
supporting information
p. 4850 - 4853
(2013/10/08)
-
- Synthesis of boron-containing primary amines
-
In this study, boron-containing primary amines were synthesized for use as building blocks in the study of peptoids. In the first step, Gabriel synthesis conditions were modified to enable the construction of seven different aminomethylphenyl boronate esters in good to excellent yields. These compounds were further utilized to build peptoid analogs via an Ugi four-component reaction (Ugi-4CR) under microwave irradiation. The prepared Ugi-4CR boronate esters were then successfully converted to the corresponding boronic acids. Finally, the peptoid structures were successfully modified by cross-coupling to aryl/heteroaryl chlorides via a palladium-mediated Suzuki coupling reaction to yield the corresponding derivatives in moderate to good yields.
- Chung, Sheng-Hsuan,Lin, Ting-Ju,Hu, Qian-Yu,Tsai, Chia-Hua,Pan, Po-Shen
-
p. 12346 - 12367
(2013/11/06)
-
- Palladium nanoparticle catalysis: Borylation of aryl and benzyl halides and one-pot biaryl synthesis via sequential borylation-Suzuki-Miyaura coupling
-
Palladium nanoparticles generated in PEG catalyze the reaction of bis(pinacolato)diboron with various aryl/benzyl halides to afford aryl/benzyl boronates in high yield. Arylboronates thus prepared, have been directly used in the Suzuki-Miyaura coupling reaction with different aryl halides and benzyl halides in a convenient one-pot, two-step solvent free green synthesis of unsymmetrical biaryls and diarylmethanes. The Royal Society of Chemistry 2012.
- Bej, Ansuman,Srimani, Dipankar,Sarkar, Amitabha
-
experimental part
p. 661 - 667
(2012/05/04)
-
- A general strategy for the perfluoroalkylation of arenes and arylbromides by using arylboronate esters and [(phen)CuRF]
-
A versatile method for the synthesis of aryl perfluoroalkanes from arenes and aryl bromides is described. Substituted arenes or aryl bromides are converted in situ to an aryl boronate ester that readily undergoes perfluoroalkylation in air with [(phen)CuRF]. A broad range of aryl bromide substrates were perfluoroalkylated in good yield for the first time. [(phen)CuCF3] is now commercially available and has been prepared on 20g scale. Copyright
- Litvinas, Nichole D.,Fier, Patrick S.,Hartwig, John F.
-
supporting information; experimental part
p. 536 - 539
(2012/02/16)
-
- Carbon-boron bond cross-coupling reaction catalyzed by -PPh2 containing palladium-indolylphosphine complexes
-
This study describes the application of indolylphosphine ligands with a diphenylphosphino moiety to the palladium-catalyzed borylation of aryl chlorides. The combination of palladium metal precursor with PPh 2-Andole-phos, which comprises an inexpensive -PPh2 group, provides highly effective catalysts for the borylation of aryl chlorides. A range of functional groups such as -CN, -NO2, -CHO, -COMe, -COOMe, and -CF3 was compatible, and the catalyst loading down to 0.025 mol % of Pd can be achieved. The Pd/PPh2-Andole-phos system is able to catalyze both borylation reaction and Suzuki-Miyaura coupling reaction in a one-pot sequential manner for the direct synthesis of biaryl compounds in excellent yields.
- Chow, Wing Kin,Yuen, On Ying,So, Chau Ming,Wong, Wing Tak,Kwong, Fuk Yee
-
experimental part
p. 3543 - 3548
(2012/06/15)
-