- Preparation, properties, and synthetic potentials of novel boronates in a fluorous version (fluorous boronates)
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(equation presented) 4a-j R = aryl, alkenyl, alkyl A series of boronic acids were attached to a fluorous tag by esterification. Functional transformations of these boronates together with the fluorous Suzuki coupling reaction illustrated their usefulness in fluorous-phase techniques.
- Chen, Dajun,Qing, Feng-Ling,Huang, Yangen
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Read Online
- An Amine Functionalized Metal-Organic Framework as an Effective Catalyst for Conversion of CO2 and Biginelli Reactions
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A highly porous and thermally stable anionic Zn(II)-framework, {[(CH3)2NH2+]2[Zn3((μ3-O))(L)2(H2O)]·4DMF·2H2O}n (1), having exposed metal sites and pendant amine groups has been synthesized adopting the solvothermal technique. This anionic 3D framework showed two-fold interpenetration with 45.1% void volume. It has a 3,6-c binodal net with rare sit 3,6-conn topology. The metal bound aqua ligand could be easily removed along with the guest molecules in the lattice upon activation to afford the desolvated framework 1′. This produced exposed metal sites that, along with the pendant amine groups incorporated in the ligand, generated a coordination space in the framework to make it an outstanding heterogeneous catalyst for the chemical fixation of CO2 with various epoxides under atmospheric pressure and in the three-component Biginelli reaction with different aldehydes, ethyl acetoacetate, and urea to afford dihydropyrimidinones.
- Verma, Ashish,De, Dinesh,Tomar, Kapil,Bharadwaj, Parimal K.
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- Remote-Controlled Release of Singlet Oxygen by the Plasmonic Heating of Endoperoxide-Modified Gold Nanorods: Towards a Paradigm Change in Photodynamic Therapy
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The photodynamic therapy of cancer is contingent upon the sustained generation of singlet oxygen in the tumor region. However, tumors of the most metastatic cancer types develop a region of severe hypoxia, which puts them beyond the reach of most therapeutic protocols. More troublesome, photodynamic action generates acute hypoxia as the process itself diminishes cellular oxygen reserves, which makes it a self-limiting method. Herein, we describe a new concept that could eventually lead to a change in the 100 year old paradigm of photodynamic therapy and potentially offer solutions to some of the lingering problems. When gold nanorods with tethered endoperoxides are irradiated at 808 nm, the endoperoxides undergo thermal cycloreversion, resulting in the generation of singlet oxygen. We demonstrate that the amount of singlet oxygen produced in this way is sufficient for triggering apoptosis in cell cultures. EPT sees the light: When gold nanorods with tethered endoperoxides are irradiated with near-infrared light, the endoperoxides undergo thermal cycloreversion, resulting in the generation of singlet oxygen. The amount of singlet oxygen generated by these nanocomposites is sufficient for triggering apoptosis in cell cultures.
- Kolemen, Safacan,Ozdemir, Tugba,Lee, Dayoung,Kim, Gyoung Mi,Karatas, Tugce,Yoon, Juyoung,Akkaya, Engin U.
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- Water-soluble polymeric photoswitching dyads impart super-resolution lysosome highlighters
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In this report, we integrated a photoswitchable quencher, a highly emissive yet pH sensitive fluorophore, and a water-soluble polymer with controlled hydrophilicity into a functional nanosystem. The photoswitching quencher is based on dithienylethene (DTE) unit, while the pH-sensitive emitter is naphthalimide (NI) unit and the water-soluble polymer is obtained from polymerization of N-isopropylacrylamide (NIPAM). Together, these three units create a novel super-resolution lysosome highlighter, although individually none can function as a lysotracker. Because the emitter is sensitive to pH, the resulting polymer becomes highly fluorescent in acidic lysosomes. In addition, photoswitching regulates the fluorescence on and off and thus enables super-resolution localization of fluorescent polymers with sub-40 nm spatial resolution in imaging subcellular organelles. Thus, the concept presented here, including the photoswitchable DTE-pH-sensitive NI dyad, is promising to guide the development of future-generation super-resolution imaging agents.
- Li, Chong,Hu, Zhe,Aldred, Matthew P.,Zhao, Ling-Xi,Yan, Hui,Zhang, Guo-Feng,Huang, Zhen-Li,Li, Alexander D. Q.,Zhu, Ming-Qiang
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Read Online
- Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water
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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
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p. 1842 - 1851
(2018/02/23)
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- Preparation method of anti-tumor drug Acalabrutinib key intermediate
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The invention relates to a preparation method of an anti-tumor drug Acalabrutinib key intermediate. The preparation method comprises the following steps: with para-bromotoluene as a raw material, generating para-toluene boric acid through a Grignard reaction; performing oxidation through a nickel catalyst and then cyclization; finally, under the effect of DMAP catalysis and EDC hydrochloride, combining 2-aminopyridine to obtain a target product N-2-pyridyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)benzamide. According to the preparation method provided by the invention, in the preparation process of N-2-pyridyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)benzamide, the use of high-pollution and high-risk solvent or catalyst is avoided, the aftertreatment is simple, the product has high purity and can be directly applied to next reaction without purification; moreover, the operation is simple, the pollution is little, and the cost is low; through an oxidation process of a relatively cheap nickel catalyst efficiently catalyzing potassium permanganate, the yield is increased, and the cost is remarkably lowered.
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Paragraph 0021; 0038; 0040; 0046; 0052; 0058; 0064; 0070
(2019/01/14)
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- A N, 6 diphenyl pyrimidine -4 - amine Bcr - Abl inhibitor and its preparation method and application (by machine translation)
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The invention discloses a N, 6 diphenyl pyrimidine - 4 - amine Bcr - Abl inhibitor and its preparation method and application, the structural formula of the inhibitor for the wherein R is a single substituent or double-substituent, substituent is alkyl or halogen; R1 As a single substituent or double-substituent, substituent is alkyl or halogen. The series of inhibitors in vitro ABL1 kinase restraining effects, and can inhibit the proliferation of tumor cells, can be used for anti-tumor pharmaceutical preparation, in particular CML (chronic granulocytic leukemia) drug. The invention provides N, 6 diphenyl pyrimidine - 4 - amine Bcr - Abl inhibitor preparation method, raw materials are apt, mild reaction conditions, the reaction process is simple in operation, reagent used and cheap. (by machine translation)
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Paragraph 0041; 0045; 0046
(2017/04/28)
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- A process for preparing carboxyl boric acid
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The invention discloses a method for preparing carboxyl phenylboronic acid. The method comprises the following steps of starting from halogenated phenylboronic acid, heating, refluxing and dehydrating in a solvent to form a tripolymer; then forming a grignard reagent of corresponding tripolymer from tripolymer and magnesium metal or isopropyl magnesium chloride; then introducing a carbon dioxide gas at low temperature or adding dry ice for reaction; after the reaction is finished, adding hydrochloric acid, regulating till pH is equal to 2-3, and hydrolyzing; and precipitating carboxyl phenylboronic acid, filtering, and drying to obtain a pure product. The method disclosed by the invention can achieve good yield on ortho-position, meta-position and para-position carboxyl phenylboronic acid, is simple in used reagent and easy and convenient to operate and prevents the generation of a large quantity of solid wastes.
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Paragraph 0022; 0023
(2017/08/25)
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- A 4 - carboxyl preparation process of boric acid (by machine translation)
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The invention discloses a 4 - carboxyl boric acid process. In order to to iodine benzoic acid as the raw material, by esterification reaction, sediment reaction and hydrolysis reaction to obtain the target product 4 - carboxyl boric acid, the total yield can reach 88.7%. The process route raw materials are cheap and easy to obtain, after-treatment is convenient, high yield, easy industrialized application. (by machine translation)
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- A process for the preparation of boric acid P-carboxyl
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The invention discloses a preparation method of p-carboxyphenylboronic acid. The preparation method comprises the steps of carrying out an amidation reaction on bromobenzoic acid and diisopropylamine to obtain a reaction intermediate 4-bromo-N,N-diisopropylbenzamide; carrying out the substitution reaction on the 4-bromo-N,N-diisopropylbenzamide at a reaction temperature ranging from -75 to -80 DEG C in a solvent which is dry tetrahydrofuran, thereby obtaining (4-(diisopropylcarbamyl)phenyl) boric acid; hydrolyzing (4-(diisopropylcarbamyl)phenyl) boric acid in the presence of lithium hydroxide monohydrate to obtain p-carboxyphenylboronic acid. The preparation method provided by the invention is high in product yield, simple and convenient to operate, low in reaction cost and applicable to industrial production.
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- A Arylheterocycle chirality bcr - abl inhibitor and its preparation method and application
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The invention discloses aromatic heterocyclic biphenyl Bcr-Abl inhibitors as well as a preparation method and application thereof. A structural formula of the inhibitors is shown in the specification, wherein in the structural formula, Ar is aromatic heterocycle; R is a mono-substituent or a di-substituent, and the substituent is alkyl or halogen. The series of inhibitors have a certain inhibiting effect on ABL1 kinase in vitro, can inhibit tumor cell proliferation and can be used for preparing antitumor drugs, especially CML (chronic myelocytic leukemia) drugs. The preparation method of the aromatic heterocyclic biphenyl Bcr-Abl inhibitors, which is provided by the invention, has the advantages of easiness in obtainment of raw materials, mild reaction conditions, simplicity in operation of reaction processes and cheap used reagents.
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Paragraph 0045
(2016/10/09)
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- A N, 6 diphenyl-pyrimidin-4-amine Bcr-Abl inhibitor and its preparation method and application
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The invention discloses N,6 diphenylpyrimidine-4-amine Bcr-Abl inhibitors as well as a preparation method and application thereof. A structural formula of the inhibitors is shown in the specification, wherein in the structural formula, R is a mono-substituent or a di-substituent, and the substituent is alkyl, halogen or tertiary amino. The series of inhibitors have a certain inhibiting effect on ABL1 kinase in vitro, can inhibit tumor cell proliferation and can be used for preparing antitumor drugs, especially CML (chronic myelocytic leukemia) drugs. The preparation method of the N,6 diphenylpyrimidine-4-amine Bcr-Abl inhibitors, which is provided by the invention, has the advantages of easiness in obtainment of raw materials, mild reaction conditions, simplicity in operation of reaction processes and cheap used reagents.
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Paragraph 0040-0043; 0044
(2016/10/31)
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- Synthesis and biological evaluation of novel aromatic-heterocyclic biphenyls as potent anti-leukemia agents
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As a continuation to our previous research, twenty-eight aromatic-heterocyclic biphenyls were designed and synthesized as novel Bcr-Abl inhibitors. The title compounds were investigated for their antiproliferative activities against wild K562 cells and Imatinib-resistant K562 cells (K562R). The results indicated that most of them exhibited potent Bcr-Abl inhibition and moderate antiproliferative potency against K562 cells. Furthermore, three compounds 3, 7 and 21 displayed moderate antiproliferative activities against K562R cells. Molecular docking indicated that 3 bound more tightly with Bcr-AblT315I compared to Bcr-AblWT. The higher affinity was consistent with its relatively promising K562R cell growth inhibition. These aromatic-heterocyclic biphenyls could be considered as novel lead compound for optimized as Bcr-AblT315I inhibitors. They provide a good starting point for the further development of novel anti-leukemia agents capable of dealing with clinical acquired resistance against Imatinib.
- Dong, Jinyun,Pan, Xiaoyan,Wang, Jinfeng,Su, Ping,Zhang, Lin,Wei, Fen,Zhang, Jie
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p. 780 - 789
(2015/08/06)
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- Expanding the structural diversity of Bcr-Abl inhibitors: Dibenzoylpiperazin incorporated with 1 H -indazol-3-amine
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A series of N,N'-dibenzoylpiperazine derivatives incorporated with 1H-indazol-3-amine have been designed, synthesized and evaluated as novel Bcr-Abl inhibitors. Several title compounds exhibited potent inhibitory activity against Bcr-Abl wild type as well as T315I mutant. Two compounds, 11a and 12c, strongly suppressed the activity of native and mutant Bcr-Abl. In particular, 11a exhibited comparable potency with that of Imatinib. It potently inhibited both Bcr-AblWT and Bcr-AblT315I with IC50 values of 0.014 μM and 0.45 μM, respectively. Furthermore, compound 11a also inhibited the proliferation of K562 leukemia cancer cells. Therefore, it could serve as promising lead compound for further optimization of Bcr-AblWT and Bcr-AblT315I inhibitors.
- Shan, Yuanyuan,Dong, Jinyun,Pan, Xiaoyan,Zhang, Lin,Zhang, Jie,Dong, Yalin,Wang, Maoyi
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p. 139 - 147
(2015/10/28)
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- Versatile Tailoring of Paddle-Wheel ZnII Metal-Organic Frameworks through Single-Crystal-to-Single-Crystal Transformations
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A new tetracarboxylate ligand having short and long arms formed 2D layer ZnII coordination polymer 1 with paddle-wheel secondary building units under solvothermal conditions. The framework undergoes solvent-specific single crystal-to-single crystal (SC-SC) transmetalation to produce 1Cu. With a sterically encumbered dipyridyl linker, the same ligand forms non-interpenetrated, 3D, pillared-layer ZnII metal-organic framework (MOF) 2, which takes part in SC-SC linker-exchange reactions to produce three daughter frameworks. The parent MOF 2 shows preferential incorporation of the longest linker in competitive linker-exchange experiments. All the 3D MOFs undergo complete SC-SC transmetalation with CuII, whereby metal exchange in different solvents and monitoring of X-ray structures revealed that bulky solvated metal ions lead to ordering of the shortest linker in the framework, which confirms that the solvated metal ions enter through the pores along the linker axis.
- Pal, Tapan K.,Neogi, Subhadip,Bharadwaj, Parimal K.
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supporting information
p. 16083 - 16090
(2015/11/03)
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- Oxygenation of Organoboronic Acids by a Nonheme Iron(II) Complex: Mimicking Boronic Acid Monooxygenase Activity
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Phenolic compounds are important intermediates in the bacterial biodegradation of aromatic compounds in the soil. An Arthrobacter sp. strain has been shown to exhibit boronic acid monooxygenase activity through the conversion of different substituted phenylboronic acids to the corresponding phenols using dioxygen. While a number of methods have been reported to cleave the C-B bonds of organoboronic acids, there is no report on biomimetic iron complex exhibiting this activity using dioxygen as the oxidant. In that direction, we have investigated the reactivity of a nucleophilic iron-oxygen oxidant, generated upon oxidative decarboxylation of an iron(II)-benzilate complex [(TpPh2)FeII(benzilate)] (TpPh2 = hydrotris(3,5-diphenyl-pyrazol-1-yl)borate), toward organoboronic acids. The oxidant converts different aryl/alkylboronic acids to the corresponding oxygenated products with the incorporation of one oxygen atom from dioxygen. This method represents an efficient protocol for the oxygenation of boronic acids with dioxygen as the terminal oxidant.
- Chatterjee, Sayanti,Paine, Tapan Kanti
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p. 9727 - 9732
(2015/11/03)
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- Expanding the structural diversity of Bcr-Abl inhibitors: Hybrid molecules based on GNF-2 and Imatinib
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In order to expand the structural diversity of Bcr-Abl inhibitors, twenty hybrids (series E and P) have been synthesized and characterized based on Imatinib and GNF-2. Their biological activities were evaluated in vitro against human leukemia cells. Most compounds exhibited potent antiproliferative activity against K562 cells, especially for compounds E4, E5 and E7. Furthermore, these new hybrids were also screened for Abl kinase inhibitory activity, and some of them inhibited Abl kinase with low micromolar IC50 values. In particular, compound P3 displayed the most potent activity with IC50 value of 0.017 μM comparable with that of Imatinib. Molecular docking studies indicated that these novel hybrids fitted well with the active site of Bcr-Abl. These results suggested the great potential of these compounds as novel Bcr-Abl inhibitors.
- Pan, Xiaoyan,Dong, Jinyun,Shao, Ruili,Su, Ping,Shi, Yaling,Wang, Jinfeng,He, Langchong
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supporting information
p. 4164 - 4168
(2015/11/03)
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- Electrophilicity and nucleophilicity of commonly used aldehydes
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The present approach for determining the electrophilicity (E) and nucleophilicity (N) of aldehydes includes a kinetic study of KMNO4 oxidation and NaBH4 reduction of aldehydes. A transition state analysis of the KMNO4 promoted aldehyde oxidation reaction has been performed, which shows a very good correlation with experimental results. The validity of the experimental method has been tested using the experimental activation parameters of the two reactions. The utility of the present approach is further demonstrated by the theoretical versus experimental relationship, which provides easy access to E and N values for various aldehydes and offers an at-a-glance assessment of the chemical reactivity of aldehydes in various reactions. the Partner Organisations 2014.
- Pratihar, Sanjay
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p. 5781 - 5788
(2014/07/22)
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- Discovery of novel Bcr-Abl inhibitors targeting myristoyl pocket and ATP site
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Bcr-Abl plays an essential role in the pathogenesis and development of chronic myeloid leukaemia (CML). Inhibition of Bcr-Abl has great potential for therapeutic intervention in CML. In order to obtain novel and potent Bcr-Abl inhibitors, twenty seven 4,6-disubstituted pyrimidines were synthesized and evaluated herein. The biological results indicated that four compounds of them (C4, C5, C16, and C23) were potent Bcr-Abl inhibitors which were comparable to positive control. Moreover, C4 and C5 displayed promising antiproliferative activity against K562 cells. The results suggested that these 4,6-disubstituted pyrimidines could serve as promising leads for further optimization of Bcr-Abl inhibitors.
- Dong, Jinyun,Lu, Wen,Pan, Xiaoyan,Su, Ping,Shi, Yaling,Wang, Jinfeng,Zhang, Jie
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p. 6876 - 6884
(2015/01/09)
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- High CO2/N2 and CO2/CH4 selectivity in a chiral metal-organic framework with contracted pores and multiple functionalities
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A metal-organic framework with chiral pores and decorated imidazole and methyl groups was constructed. Upon activation, this MOF undergoes a pore contraction and shows very high selectivity for CO2/N2 and CO2/CH4, indicating a synergistic effect of dynamic pores and functional groups. the Partner Organisations 2014.
- Lv, Xiaoxia,Li, Liangjun,Tang, Sifu,Wang, Chao,Zhao, Xuebo
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supporting information
p. 6886 - 6889
(2014/06/23)
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- Synthesis of 2-amino-4-(methoxycarbonyl)phenylboronic acid hydrochloride, a key intermediate for the synthesis of quinolines derivatives
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A practical and efficient process for the synthesis in good yield of 2-amino-4-(methoxycarbonyl)phenylboronic acid hydrochloride from p-bromo toluene has been developed via borylation, oxidation, nitration, esterification and hydrogenation.
- Xue, Feng,Li, Chang-Gong,Zhu, Yong,Lou, Tian-Jun
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p. 719 - 721
(2015/02/02)
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- METHOD FOR THE PRODUCTION OF BORONIC ACIDS CARRYING CYANOALKYL, CARBOXYL AND AMINOCARBONYL GROUPS AND THEIR DERIVATIVES
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A process for the manufacture of aminocarbonyl boronic acids of formula (IV) by converting the compounds of formula (III) with a Br?nsted base Y(OH)n in a solvent or a solvent mixture, in which Z represents an optionally substituted arylene, heteroarylene, alkene, heteroalkene, alkylidene, heteroalkylidene, alkenylidene, heteroalkenylidene, alkynylidene, arylalkylene, heteroarylalkylene, arylheteroalkylene, heteroarylheteroalkylene, alkylheteroarylene, heteroalkylheteroarylene, or alkylarylene group; Y represents a metal or ammonium cation of valence n with 0n5; and B represents boronic acid, boronic acid ester, or a borate, or a boronic acid anhydride. The aminocarbonyl boronic acids of formula (IV) can be further hydrolyzed to form the carboxy boronic acid of formula (V).
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Page/Page column 4
(2009/12/05)
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- Predicting the structure of supramolecular dendrimers via the analysis of libraries of AB3 and constitutional isomeric AB2 biphenylpropyl ether self-assembling dendrons
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The synthesis of 4′-hydroxy-4-biphenylpropionic, 3′,4′- dihydroxy-4-biphenylpropionic, 3′,5′-dihydroxy-4-biphenylpropionic, and 3′,4′,5′-trihydroxy-4-biphenylpropionic methyl esters via three efficient and modular strategies including one based on Ni-catalyzed borylation and sequential cross-coupling is reported. These building blocks were employed in a convergent iterative approach to the synthesis of one library of 3,4,5-trisubstituted and two libraries of constitutional isomeric 3,4- and 3,5-disubstituted biphenylpropyl ether dendrons. Structural and retrostructural analysis of supramolecular dendrimers revealed that biphenylpropyl ether dendrons self-assemble and self-organize into the same periodic lattices and quasi-periodic arrays observed in previously reported libraries, but with larger dimensions, different mechanisms of self-assembly, and improved solubility, thermal, acidic, and oxidative stability. The different mechanisms of self-assembly led to the discovery of two new supramolecular structures. The first represents a new banana-like lamellar crystal with a four layer repeat. The second is a giant vesicular sphere self-assembled from 770 dendrons that exhibits an ultrahigh molar mass of 1.73 × 106 g/mol. Thus, the enhanced size of the self-assembled structures constructed from biphenylpropyl ether dendrons permitted for the first time discrimination of various molecular mechanisms of spherical self-assembly and elaborated a continuum between small filled spheres and very large hollow spheres that is dictated by the primary structure of the dendron. The comparative analysis of libraries of biphenylpropyl ether dendrons with the previously reported libraries of benzyl-, phenylpropyl-, and biphenyl-4-methyl ether dendrons demonstrated biomimetic self-assembly wherein the primary structure of the dendron and to a lesser extent the structure of its repeat unit determines the supramolecular tertiary structure. A "nanoperiodic table" of self-assembling dendrons and supramolecular dendrimers that allows the prediction of the general features of tertiary structures from primary structures was elaborated.
- Rosen, Brad M.,Wilson, Daniela A.,Wilson, Christopher J.,Peterca, Mihai,Won, Betty C.,Huang, Chenghong,Lipski, Linda R.,Zeng, Xiangbing,Ungar, Goran,Heiney, Paul A.,Percec, Virgil
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scheme or table
p. 17500 - 17521
(2010/03/25)
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- One-pot generation of lithium (lithiophenyl)trialkoxyborates from substituted dihalobenzenes (Hal = Br, I) and their derivatization with electrophiles
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The simple one-pot approach to synthetically useful phenyltrialkoxyborates bearing lithium at the phenyl ring has been developed starting with 1,3- and 1,4-diiodobenzene, as well as several activated dibromobenzenes and bromoiodobenzenes. The general sequence of transformations involves halogen-lithium exchange by using nBuLi and subsequent boronation with a trialkylborate. The resulting lithium (halophenyl) trialkoxyborates were then subjected to halogen-lithium exchange in situ with a second equivalent of nBuLi to give dianionic lithium (lithiophenyl)trialkoxyborates. Treatment with selected electrophiles afforded substituted arylboronic acids and/or their pinacol esters as final products in moderate-to-good yields. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Kurach, Pawel,Lulinski, Sergiusz,Serwatowski, Janusz
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experimental part
p. 3171 - 3178
(2009/05/30)
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- Multistep synthesis of complex boronic acids from simple MIDA boronates
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Due to its sensitivity to most synthetic reagents, it is typically necessary to introduce the boronic acid functional group just prior to its utilization. Overcoming this important limitation, we herein report that air- and chromatographically stable MIDA boronates are compatible with a wide range of common reagents which enables the multistep synthesis of complex boronic acid building blocks from simple B-containing starting materials. X-ray and variable temperature NMR studies link the unique stability of MIDA boronates to a kinetic inaccessibility of the potentially reactive boron p-orbital and/or nitrogen lone pair. These findings were collectively harnessed to achieve a short and modular total synthesis of (+)-crocacin C via the iterative cross-coupling of a structurally complex, MIDA-protected haloboronic acid building block. Copyright
- Gillis, Eric P.,Burke, Martin D.
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supporting information; experimental part
p. 14084 - 14085
(2009/03/11)
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- Hierarchical self-assembly of p-terphenyl derivative with dumbbell-like amphiphilic and rod-coil characteristics
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As water is gradually added, a p-terphenyl derivative with dumbbell-like amphiphilic and rod-coil characteristics can hierarchically self-assemble to metastable rectangle columns architecting sheets first and then to stable quasi-hexagonal columns architecting rolled sheets, and finally to rod-like nanostructures in MeOH/H2O solution. Interestingly, the formed sheet, rolled sheet, and nanorod possess blue-light emitting property.
- Zhou, Qilong,Chen, Ting,Zhang, Jintao,Wan, Lijun,Xie, Ping,Han, Charles C.,Yan, Shouke,Zhang, Rongben
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p. 5522 - 5526
(2008/12/22)
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- Expanding the structural diversity of self-assembling dendrons and supramolecular dendrimers via complex building blocks
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The design and synthesis of the first examples of AB4 and AB5 dendritic building blocks with complex architecture are reported. Structural and retrostructural analysis of supramolecular dendrimers self-assembled from hybrid dendrons based on different combinations of AB 4 and AB5 building blocks with AB2 and AB 3 benzyl ether dendrons demonstrated that none of these new hybrid dendrons exhibit the previously encountered conformations of libraries of benzyl ether dendrons. These hybrid dendrons enabled the discovery of some highly unusual tapered and conical dendrons generated by the intramolecular backfolding of their repeat units and of their apex. The new back-folded tapered dendrons have double thickness and self-assemble into pine-tree-like columns exhibiting a long-range 7/2 helical order. The back-folded conical dendrons self-assemble into spherical dendrimers. Non-back-folded truncated conical dendrons were also discovered. They self-assemble into spherical dendrimers with a less densely packed center. The discovery of dendrons displaying a novel crown-like conformation is also reported. Crown-like dendrons self-assemble into long-range 5/1 helical pyramidal columns. The long-range 7/2 and 5/1 helical structures were established by applying, for the first time, the helical diffraction theory to the analysis of X-ray patterns obtained from oriented fibers of supramolecular dendrimers.
- Percec, Virgil,Won, Betty C.,Peterca, Mihai,Heiney, Paul A.
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p. 11265 - 11278
(2008/03/14)
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- Substituted phenyl derivatives, their preparation and use
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The present invention discloses compounds having the formula wherein the substituents are defined in the application. The compounds are useful as chloride channel blockers.
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- DIARYLUREA DERIVATIVES AND THEIR USE AS CHLORIDE CHANNEL BLOCKERS
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The present invention relates to novel diarylurea derivatives useful as chloride channel blockers. In other aspects the invention relates to the use of these compounds in a method for therapy, such as for the treatment of bone metabolic diseases, diseases responsive to modulation of the mast cell or basophil activity, diseases responsive to inhibition of angiogenesis, or sickle cell anaemia, and to pharmaceutical compositions comprising the compounds of the invention.
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- (BIS)sulfonamide derivatives
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The present invention provides (bis) sulfonamide derivatives of formula (I) useful for potentiating glutamate receptor function in a mammal and therefore, useful for treating a wide variety of conditions, such as psychiatric and neurological disorders.
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- Process for the preparation of substituted phenylboronic acids
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Compounds of the formula (I) in which Q1and Q2are each OH or form a trimeric boric anhydride, Z is CHO, CH2Y, X or a protected aldehyde group, and X is CN, COOH, COCl, CONH2or C(OR)3, and Y is OH or NH2, and Z is in the o-, m- or p-position to the boronic acid radical, are prepared by a) reacting a compound of the formula (II) ?with Mg in the presence of an anthracene compound and, if desired, a transition-metal halide and, if desired, an Mg halide or in the presence of a transition-metal halide and, if desired, an Mg halide, to give the corresponding arylmagnesium chloride, b) reacting the latter with a borate of the formula B(OR′)3and hydrolyzing the product, with removal of the aldehyde protecting group, c) and, if desired, oxidizing or reducing the free aldehyde group.
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- N-substituted sulfonamide derivatives
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The present invention provides certain N-substituted sulfonamide derivatives useful for potentiating glutamate receptor function in a mammal and therefore, useful for treating a wide variety of conditions, such as psychiatric and neurological disorders.
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- Synthesis of some para-functionalized phenylboronic acid derivatives
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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
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p. 2669 - 2676
(2007/10/03)
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- An improved protocol for the preparation of 3-pyridyl- and some arylboronic acids
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3-Pyridylboronic acid was prepared in high yield and bulk quantity from 3-bromopyridine via a protocol of lithium-halogen exchange and "in situ quench". This technique was further studied and evaluated on other aryl halides in the preparation of arylboronic acids.
- Li, Wenjie,Nelson, Dorian P.,Jensen, Mark S.,Hoerrner, R. Scott,Cai, Dongwei,Larsen, Robert D.,Reider, Paul J.
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p. 5394 - 5397
(2007/10/03)
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- Gels and multilayer surface structures from boronic acid containing polymers
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Boronic acid containing polymers are used to form bioinert gels and multilayer surface structures. These polymers form crosslinked hydrogels, which are highly swollen in water. The crosslinking can either be chemical or physical. Water soluble polymers containing boronic acid groups, such as phenylboronic acid (PBA), can be physically crosslinked by mixing the polymers in water with other polymers containing hydroxyls or carboxylic acids. Alternatively, surfaces can be treated by stepwise incubation with a solution of the boronic acid containing polymer, followed by incubation with a solution of a diol or carboxylic acid containing polymer. Many successive layers can be generated, increasing the thickness of the formed structure at each step. The bioinert gel or surface coating can be used for passivating the surfaces of medical implants (especially those based on transplanted tissue), or for passivating the surfaces of tissues in situ, decreasing the incidence or severity of such pathologic conditions as the formation of post-surgical adhesions, and thrombosis following angioplasty.
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- Substituted phenyl derivatives, their preparation and use
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The present invention discloses compounds having the formula wherein the substituents are defined in the application. The compounds are useful as chloride channel blockers.
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- Substituted phenyl derivatives, their preparation and use
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A compound having the formula (I) or a pharmaceutically acceptable salt thereof where the variables are defined in the specification are useful in the treatment of sickle-cell anemia.
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- Sulphonamide derivatives
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Glutamate receptor function in a mammal may be potentiated using an effective amount of a compound of formulaR1—L—NHSO2R2??Iin whichR1 represents an unsubstituted or substituted aromatic or heteroaromatic group;R2 represents (1-6C)alkyl, (3-6C)cycloalkyl, (1-6C)fluoroalkyl, (1-6C)chloroalkyl, (2-6C)alkenyl, (1-4C)alkoxy(1-4C)alkyl, phenyl which is unsubstituted or substituted by halogen, (1-4C)alkyl or (1-4C)alkoxy, or a group, of formula R3R4N in which R3 and R4 each independently represents (1-4C)alkyl or, together with the nitrogen atom to which they are attached form an azetidinyl, pyrrolidinyl, piperidinyl, morpholino, piperazinyl, hexahydroazepinyl or octahydroazocinyl group; andL represents a (2-4C)alkylene chain which is unsubstituted or substituted by one or two substituents selected independently from (1-6C)alkyl, aryl(1-6C)alkyl, (2-6C)alkenyl, aryl(2-6C)alkenyl and aryl, or by two substituents which, together with the carbon atom or carbon atoms to which they are attached form a (3-8C)carbocyclic ring;and pharmaceutically acceptable salts thereof.Also disclosed are compounds of formula I, processes for preparing them and pharmaceutical compositions containing them.
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- Labelled boronic acid derivatives
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The invention provides novel labelled boronic acid conjugates of formula STR1 (wherein V is a reporter moiety; W2 is a bond or an organic linker moiety; W1 is a *SO2 NR2, *CON2 or *CH2 N≈R2 2 group bound at the *-marked atom to the phenyl ring; R1 is hydrogen or an electron withdrawing substituent group; and each R2 independently is hydrogen or an optionally hydroxylated and optionally C1-6 -alkoxylated C1-6 -alkyl group) and salts thereof, e.g. for use in assays for cis-diols such as glycated blood proteins, having enhanced water-solubility and storage stability.
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