- A Ni0 σ-Borane Complex Bearing a Rigid Bidentate Borane/Phosphine Ligand: Boryl Complex Formation by Oxidative Dehydrochloroborylation and Catalytic Activity for Ethylene Polymerization
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While of interest, synthetically feasible access to boryl ligands and complexes remains limited, meaning such complexes remain underexploited in catalysis. For bidentate boryl ligands, oxidative addition of boranes to low-valent IrI or Pt0 are the only examples yet reported. As part of our interest in developing improved group 10 ethylene polymerization catalysts, we present here an optimized synthesis of a novel, rigid borane/phosphine ligand and its Ni0 σ-borane complex. From the latter, an unprecedented oxidative dehydrochloroborylation, to give a NiII boryl complex, was achieved. Furthermore, this new B/P ligand allowed the nickel-catalyzed polymerization of ethylene, which suggests that Ni0 σ-hydroborane complexes act as masked NiII boryl hydride reagents.
- Nozaki, Kyoko,Seidel, Falk William
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supporting information
(2021/12/23)
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- The Trityl-Cation Mediated Phosphine Oxides Reduction
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Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
- Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
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supporting information
p. 3035 - 3043
(2021/05/10)
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- Preparation method and application of thioimino quinoline metal compound
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The invention relates to a preparation method of a thioimino quinoline chromium metal compound and application of the thioimino quinoline chromium metal compound in olefin polymerization. According to the invention, a quinoline skeleton is introduced, a novel metal compound of thioimino quinoline chromium is designed and synthesized, and the space effect and the electronic effect of the metal catalyst with the structure can be conveniently regulated and controlled by changing the substituent group of the ligand, so that different catalytic properties are realized. The novel metal compound of thioimino quinoline chromium reported by the invention has the characteristics of cheap and easily available raw materials, simple synthetic route and high product yield, and in the presence of MAO, all chromium complexes show medium to high activity to ethylene polymerization, and the activity is up to 9.17 * 10 g.mol (Cr). h. Therefore, the novel metal compound of thioimino quinoline chromium reported by the invention has original innovation, and can enhance the competitive power of the polyolefin high polymer material technology market in China.
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Paragraph 0017-0018
(2021/11/21)
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- Chiral Memory in Silyl-Pyridinium and Quinolinium Cations
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Pyridine- and quinoline-stabilized silyl cations have been prepared, and their structure in condensed phases unambiguously assigned using 1H, 13C, 15N, 29Si, and 1H DOSY NMR as well as X-ray diffraction studies. Solid state structures thus show in both cases a stabilization of the cationic silicon center through an N-Si interaction and formation of a highly strained four-membered ring system. Chiral memory at the silicon atom in these heterocycle-stabilized silyl cations was also established, leading to various levels of selectivity depending on the nature of the heterocycle. Lowest energy conformations of the starting silanes obtained through DFT calculations, along with the isolation and characterization of the Si-centered chiral silyl cation intermediates, finally allowed to propose a plausible hypothesis as to the configurational stability of these silyl cations.
- Fernandes, Anthony,Laye, Claire,Pramanik, Suman,Palmeira, Dayvson,Pekel, ?zgen ?mür,Massip, Stéphane,Schmidtmann, Marc,Müller, Thomas,Robert, Frédéric,Landais, Yannick
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supporting information
p. 564 - 572
(2020/01/09)
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- Synthesis of a T-Shaped Cobalt(I) Complex and Its Dinitrogen Adduct
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The coordination chemistry of the new NNP pincer ligand framework (QuiNacNacP) is explored with cobalt. Upon treatment of the cobalt(II) complex Co[QuiNacNacP]Cl with KC8, the formation of cobalt(I) dinitrogen complex Co[QuiNacNacP]N2 was observed. Co[QuiNacNacP]N2 crystallizes as a square planar (S = 0) complex with an essentially unactivated N2 ligand. In solution, the dinitrogen complex is in equilibrium with the paramagnetic T-shaped complex Co[QuiNacNacP] (S = 1). The ability of Co[QuiNacNacP]Cl to act as a catalyst precursor in the reductive silylation of dinitrogen was also briefly explored. Reaction of ≈ 1000 equivalents KC8 with ≈ 1500 equivalents Me3SiCl (relative to Co[QuiNacNacP]Cl) under 1 atm of N2 furnished roughly 40 equivalents of N(SiMe3)3.
- Sanz, Corey A.,Stein, Carolin A. M.,Fryzuk, Michael D.
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p. 1465 - 1471
(2020/02/11)
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- Highly Enantioselective Iron-Catalyzed cis-Dihydroxylation of Alkenes with Hydrogen Peroxide Oxidant via an FeIII-OOH Reactive Intermediate
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The development of environmentally benign catalysts for highly enantioselective asymmetric cis-dihydroxylation (AD) of alkenes with broad substrate scope remains a challenge. By employing [FeII(L)(OTf)2] (L=N,N′-dimethyl-N,N′-bis(2-methyl-8-quinolyl)-cyclohexane-1,2-diamine) as a catalyst, cis-diols in up to 99.8 % ee with 85 % isolated yield have been achieved in AD of alkenes with H2O2as an oxidant and alkenes in a limiting amount. This “[FeII(L)(OTf)2]+H2O2” method is applicable to both (E)-alkenes and terminal alkenes (24 examples >80 % ee, up to 1 g scale). Mechanistic studies, including18O-labeling, UV/Vis, EPR, ESI-MS analyses, and DFT calculations lend evidence for the involvement of chiral FeIII-OOH active species in enantioselective formation of the two C?O bonds.
- Zang, Chao,Liu, Yungen,Xu, Zhen-Jiang,Tse, Chun-Wai,Guan, Xiangguo,Wei, Jinhu,Huang, Jie-Sheng,Che, Chi-Ming
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supporting information
p. 10253 - 10257
(2016/08/24)
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- Reduction of quinolines to 1,2,3,4-tetrahydroquinolines with hydrosilane/ethanol catalyzed by TiO2-supported gold nanoparticles under solvent free conditions
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Gold nanoparticles supported on TiO2 (1 mol%) catalyze the reduction of a series of functionalized quinolines into 1,2,3,4-tetrahydroquinolines using hydrosilanes/ethanol (hydride/proton) as the reductant system. A typical reaction requires 4 molar equivalents of phenyldimethylsilane (reductant of choice), 4 molar equivalents of ethanol as a reagent and heating to 70 °C under solvent free conditions. The isolated yields are moderate to excellent and in certain cases the reaction rate is exceedingly fast. Mechanistic analysis revealed the stereoselective addition of two hydrides (from hydrosilane) on positions C2 and C4 of the quinoline ring and two protons (from ethanol) on positions C3 and the nitrogen atom.
- Louka, Anastasia,Gryparis, Charis,Stratakis, Manolis
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- Nucleotides and aptamers containing boronic acid groups having biased binding to glycosylated proteins, and uses thereof
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The present disclosure encompasses oligonucleotide aptamers selectively binding a target glycosylated polypeptide or protein, and having biased affinity for the glycan through a boronic acid linked to a nucleosidic base of a nucleotide(s). The disclosure further encompasses methods for isolating an aptamer(s) selectively binding a target glycosylated polypeptide, where, from a population of randomized oligonucleotides that have at least one nucleotide having a boronic acid label linked to a base, is selected a first subpopulation of aptamers binding to the target glycosylated polypeptide or protein. This subpopulation is then amplified without using boronic acid-modified TTP, and amplification products not binding to a target glycosylated polypeptide or protein are selected. The second subpopulation of aptamers is then amplified using boronic acid-modified TTP to provide a population of boronic acid-modified aptamers capable of selectively binding to a glycosylation site of a target polypeptide or protein. Other aspects of the disclosure encompass methods for the use of the modified aptamers to detect glycosylated species of a polypeptide or protein.
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- 8-SUBSTITUTED QUINOLINES AND RELATED ANALOGS AS SIRTUIN MODULATORS
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Provided herein are 8-substituted quinolines and related analogues as sirtuin-modulating compounds of Structural Formula (I) and methods of use thereof. The sirtuin-modulating compounds may be used for increasing the lifespan of a cell, and treating and/or preventing a wide variety of diseases and disorders including, for example, diseases or disorders related to aging or stress, diabetes, obesity, neurodegenerative diseases, cardiovascular disease, blood clotting disorders, inflammation, cancer, and/or flushing as well as diseases or disorders that would benefit from increased mitochondrial activity. Also provided are compositions comprising a sirtuin-modulating compound in combination with another therapeutic agent.
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Page/Page column 116; 117
(2010/09/18)
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- The synthesis and biological evaluation of quinolyl-piperazinyl piperidines as potent serotonin 5-HT1A antagonists
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As part of an effort to identify 5-HT1A antagonists that did not possess typical arylalkylamine or keto/amido-alkyl aryl piperazine scaffolds, prototype compound 10a was identified from earlier work in a combined 5-HT 1A antagonist/SSRI program. This quinolyl-piperazinyl piperidine analogue displayed potent, selective 5-HT1A antagonism but suffered from poor oxidative metabolic stability, resulting in low exposure following oral administration. SAR studies, driven primarily by in vitro liver microsomal stability assessment, identified compound 10b, which displayed improved oral bioavailability and lower intrinsic clearance. Further changes to the scaffold (e.g., 10r) resulted in a loss in potency. Compound 10b displayed cognitive enhancing effects in a number of animal models of learning and memory, enhanced the antidepressant-like effects of the SSRI fluoxetine, and reversed the sexual dysfunction induced by chronic fluoxetine treatment.
- Childers, Wayne E.,Havran, Lisa M.,Asselin, Magda,Bicksler, James J.,Chong, Dan C.,Grosu, George T.,Shen, Zhongqi,Abou-Gharbia, Magid A.,Bach, Alvin C.,Harrison, Boyd L.,Kagan, Natasha,Kleintop, Teresa,Magolda, Ronald,Marathias, Vasilios,Robichaud, Albert J.,Sabb, Annmarie L.,Zhang, Mei-Yi,Andree, Terrance H.,Aschmies, Susan H.,Beyer, Chad,Comery, Thomas A.,Day, Mark,Grauer, Steven M.,Hughes, Zoe A.,Rosenzweig-Lipson, Sharon,Platt, Brian,Pulicicchio, Claudine,Smith, Deborah E.,Sukoff-Rizzo, Stacy J.,Sullivan, Kelly M.,Adedoyin, Adedayo,Huselton, Christine,Hirst, Warren D.
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experimental part
p. 4066 - 4084
(2010/08/06)
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- Design, synthesis, and evaluation in vitro of quinoline-8-carboxamides, a new class of poly(adenosine-diphosphate-ribose)polymerase-1 (PARP-1) inhibitor
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Poly(ADP-ribose)polymerase-1 is an important target enzyme in drug design; inhibitors have a wide variety of therapeutic activities. A series of quinoline-8-carboxamides was designed to maintain the required pharmacophore conformation through an intramolecular hydrogen bond. 3-Substituted quinoline-8-carboxamides were synthesized by Pd-catalyzed couplings (Suzuki, Sonogashira, Stille) to 3-iodoquinoline-8-carboxamide, an efficient process that introduces diversity in the final step. 2-Substituted quinoline-8-carboxamides were prepared by selective Pd-catalyzed couplings at the 2-position of 2,8-dibromoquinoline, followed by lithium-bromine exchange of the intermediate 2-(alkyl/aryl)-8-bromoquinolines and reaction with trimethylsilyl isocyanate. The intramolecular hydrogen bond was confirmed by X-ray and by NMR. The SAR of the 3-substituted compounds for inhibition of human recombinant PARP-1 activity showed a requirement for a small narrow group. Substituents in the 2-position increased potency, with the most active 2-methylquinoline-8-carboxamide having IC50 = 500 nM (IC50 = 1.8 μM for 5-aminoisoquinolin-1- one (5-AIQ, a standard water-soluble inhibitor)).
- Lord, Anna-Marie,Mahon, Mary F.,Lloyd, Matthew D.,Threadgill, Michael D.
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supporting information; experimental part
p. 868 - 877
(2009/11/30)
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- QUINOLINE DERIVATIVES WITH AFFINITY FOR THE 5-HT2B RECEPTOR
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The present invention relates to 8-[4-(1,1 -dioxidotetrahydro-2H-thiopyran-4-yl)-1- piperazinyl]-2-methylquinoline or a pharmaceutically acceptable salt thereof (compounds of formula (I)) which bind to the 5-HT2B receptor and are capable of interfering with the effects of 5-hydroxytryptamine (5-HT) at the 5-HT2B receptor; to pharmaceutical compositions containing them; and to the use of such compounds in therapy.
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Page/Page column 14
(2009/07/25)
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- Water Soluble Boronic Acid Fluorescent Reporter Compounds and Methods of Use Thereof
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Described herein are boronic acid fluorescent compounds and methods of use thereof.
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