- Synthesis, crystal structure and solid state photoluminescence of [Pt(trpy)(C{triple bond, long}CPh)]SbF6 (trpy=2,2′:6′,2″-terpyridine)
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The synthesis and characterisation of an orange polymorph of [Pt(trpy)(C{triple bond, long}CPh)]SbF6 is described where trpy = 2,2′:6′,2″-terpyridine. An X-ray crystal structure determination at 293 K reveals that the cations are planar and stacked head-to-tail with alternating Pt?Pt distances of 3.604(1) and 4.412(1) ?. The perpendicular distances between successive cation planes are constant along the stack at a value of 3.33 ?. Crystal structure determinations at 240 and 200 K show that reducing the temperature to 200 K has no significant effect on the cation arrangement. However, below 200 K there is a phase change that we have not been able to characterise, but which has an effect on the solid state photoluminescence exhibited by [Pt(trpy)(C{triple bond, long}CPh)]SbF6. Thus, whereas at temperatures of ≥200 K, a broad peak with two components at ca. 566 and 597 nm is observed, below 200 K a longer wavelength peak develops that red-shifts as the temperature is lowered [λ(em)max = 637 nm at 80 K]. We assign the ≥200 K emission as 3MLLCT in origin, since the X-ray data show that ligand-ligand (LL) and not metal-metal (MM) interactions are important at T ≥ 200 K. On the other hand, the long wavelength emission observed below 200 K is typical of 3MMLCT emission, suggesting that the phase change leads to dz2 (Pt) s(-) dz2 (Pt) orbital interactions. Of particular interest is that the cation exhibits 3MLCT emission in dichloromethane that maximizes at 619 nm, i.e., the high temperature solid state emission occurs at a shorter wavelength, an unexpected result since intermolecular interactions in the solid usually cause the emission to occur at longer wavelengths. A possible explanation for this unexpected result is given.
- Büchner, Riaan,Field, John S.,Haines, Raymond J.,Ledwaba, Lesibana P.,McGuire Jr., Robert,McMillin, David R.,Munro, Orde Q.
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- A Drastic Effect of TEMPO in Zinc-Catalyzed Stannylation of Terminal Alkynes with Hydrostannanes via Dehydrogenation and Oxidative Dehydrogenation
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With a system consisting of a catalytic zinc Lewis acid, pyridine, and TEMPO in a nitrile medium, terminal alkynes coupled with HSnBu3, providing alkynylstannanes with structural diversity. The resulting alkynylstannane, without being isolated, could be directly used for Pd- and Cu-catalyzed transformations to deliver internal alkynes and more intricate tin-atom-containing molecules. Mechanistic studies indicated that TEMPOSnBu3 formed in situ from TEMPO and HSnBu3 works to stannylate the terminal alkyne in collaboration with the zinc catalyst, and that both of dehydrogenation and oxidative dehydrogenation processes are uniquely involved in a single reaction. (Figure presented.).
- Kai, Yuichi,Oku, Shinya,Sakurai, Kyoko,Tani, Tomohiro,Tsuchimoto, Teruhisa
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supporting information
(2019/08/21)
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- Catalytic Dehydrogenative Stannylation of C(sp)-H Bonds Involving Cooperative Sn-H Bond Activation of Hydrostannanes
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The catalytic generation of a stannylium-ion-like tin electrophile by heterolytic cleavage of the Sn-H bond in hydrostannanes at the Ru-S bond of Ohki-Tatsumi complexes is reported. Reacting these activated hydrostannanes with terminal acetylenes does not lead to hydrostannylation of the C-C triple bond but to dehydrogenative stannylation of the alkyne terminus. The scope of this rare direct C(sp)-H bond stannylation with hydrostannanes is broad, and a mechanism involving a β-tin-stabilized vinyl cation likely having a bridged structure is presented.
- Forster, Francis,Rendón López, Victoria M.,Oestreich, Martin
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supporting information
p. 1259 - 1262
(2018/02/09)
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- Pyrimidine or pyridine pyridine ketone compound and its preparation method and application (by machine translation)
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The invention discloses a kind of type I of the pyrimidine or pyridine pyridine ketone compound and its preparation and application, which belongs to the technical field of pharmaceutical preparation. The compounds have high-efficient and selectively inhibit the cell cycle dependent kinases (Cdks) CDK4 and CDK6 active, and then by inhibiting CDK4/CDK6 prevent tumor cell division. Therefore, the compounds of this invention can be used for CDK4 and CDK6 the involved in cell cycle control disorders result in various diseases, especially suitable for the treatment of malignant tumors. (by machine translation)
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Paragraph 0270
(2016/10/09)
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- PYRIDINE DERIVATIVES AND APPLICATION OF ANTI-MACOBACTERIUM THEREOF
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The present invention provides a series of pyridine derivatives and their preparation method and application thereof. The series of pyridine derivatives can be applied to treating mycobacterium-related diseases, especially to treatments of fatal mycobacterium-related diseases. The fatal diseases may be related to mycobacterium tuberculosis, mycobacterium bovis, mycobacterium avium, and mycobacterium marinum.
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Paragraph 0284; 0285
(2016/10/08)
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- Synthesis, characterization and photovoltaic properties of azadipyrromethene-based acceptors: Effect of pyrrolic substituents
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Azadipyrromethene derivatives are conjugated molecules with high absorptivity in the visible to near-IR region and high electron affinity that have great potential as electron acceptors for solar harvesting applications. To fully take advantage of these m
- Senevirathna, Wasana,Liao, Jia-Yu,Mao, Zhenghao,Gu, Jun,Porter, Matthew,Wang, Chunlai,Fernando, Roshan,Sauv, Genevive
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p. 4203 - 4214
(2015/03/04)
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- Arylacetylene-substituted naphthalene diimides with dual functions: Optical waveguides and n-type semiconductors
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New arylacetylene-substituted naphthalene diimides (NDIs) 1-6, with both light-emitting and semiconducting functions, are reported. Among them, the crystal structure of 1 was determined. On the basis of their reduction potentials and thin-film absorption
- Li, Yonghai,Zhang, Guanxin,Zhang, Wei,Wang, Jianguo,Chen, Xin,Liu, Zitong,Yan, Yongli,Zhao, Yongsheng,Zhang, Deqing
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supporting information
p. 3207 - 3214
(2015/02/19)
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- One-pot transformation of Ph2P(O)-protected ethynes: Deprotection followed by transition metal-catalyzed coupling
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Ph2P(O)-protected ethynes were successfully transformed to arylethynes in one-pot manner through t-BuOK-catalyzed deprotection followed by Sonogashira coupling with aryl halide. The arylethynes were obtained similarly by Ph2P(O)-deprotection, stannylation of the resulting terminal ethynes, and Migita-Kosugi-Stille coupling. Deprotection followed by intramolecular Eglinton coupling could be carried out in one-pot to provide cyclic butadiynes.
- Peng, Lifen,Xu, Feng,Suzuma, Yoshinori,Orita, Akihiro,Otera, Junzo
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p. 12802 - 12808
(2014/01/17)
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- Synthesis and reactivity of aryl(alkynyl)iodonium salts
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The first practical, yet simple, preparation of aryl(alkynyl)iodonium trifluoroacetate salts is described. The generic nature of this synthetic method has allowed the production of a range of aryl(alkynyl)iodonium trifluoroacetate salts with independent variation of both the alkynyl and aryliodo groups in yields of 30-85 %. Application of these new reagents to the synthesis of a series of 2-arylfuro[3,2-c]pyridines (40-64 %) highlights the potential of this class of materials as precursors to bioactive heterocyclic structures. These experiments have also demonstrated that, in this case, the effect of the aryliodo group on the reaction is negligible.
- Dixon, Luke I.,Carroll, Michael A.,Gregson, Thomas J.,Ellames, George J.,Harrington, Ross W.,Clegg, William
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supporting information
p. 2334 - 2345
(2013/05/21)
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- Stille coupling involving bulky groups feasible with gold cocatalyst
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Gold shuttle: Bulky groups, which will not (or only very sluggishly) undergo Stille coupling with stannanes and inexpensive ligands, can be efficiently coupled using bimetallic catalysis. A gold cocatalyst serves as an efficient shuttle to convey the bulky group from tin to palladium by reducing the steric crowding in the transition-states (see scheme). Copyright
- Delpozo, Juan,Carrasco, Desiree,Perez-Temprano, Monica H.,Garcia-Melchor, Max,Alvarez, Rosana,Casares, Juan A.,Espinet, Pablo
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supporting information
p. 2189 - 2193
(2013/04/10)
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- Direct synthesis of alkynylstannanes: ZnBr2 catalyst for the reaction of tributyltin methoxide and terminal alkynes
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Metal hopping: Various alkynylstannanes were synthesized by the direct reaction of Bu3SnOMe with terminal alkynes at room temperature in the presence of a ZnBr2 catalyst. Rather than acting as a Lewis acid, ZnBr2 was transmetalated with Bu3SnOMe to give Zn(OMe)2, which is key to the catalytic reaction. Copyright
- Kiyokawa, Kensuke,Tachikake, Nodoka,Yasuda, Makoto,Baba, Akio
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p. 10393 - 10396
(2011/12/04)
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- A convenient short cut from aromatic iodides to alkynylstannanes and their use for the straightforward preparation of polyacetylene and polymetallaacetylene polymers
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The palladium-catalyzed cross-coupling reaction (Stille coupling) of aromatic iodides Ar-I and tributyl(ethynyl)tin Bu3SnC≡CH form the aromatic acetylides Ar-C≡CH and the side product tributyltin iodide Bu3SnI in equimolar amount. In situ addition of lithium diisopropylamide (LDA) to this crude mixture directly affords the tributyl(ethynyl)tin aromatics Ar-C≡C-SnBu3 in high yield. In the case of the bis(iodoaromatic) I-Ar-I (Ar = phenyl, thiophene), this straightforward transformation affords the corresponding bis[tributyl(ethynyl)tin]derivative Bu3Sn-C≡C-Ar-C≡C-SnBu3. In the presence of Pd this latter species can be directly reacted with a second bis(iodoaromatic) or a bis(metaliodide) unit to form acetylenic and metallaacetylenic polymers with tailored monomer units inserted in a stereoregular polymer chain.
- Antonelli, Eleonora,Rosi, Patrizia,Lo Sterzo, Claudio,Viola, Egidio
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p. 210 - 222
(2007/10/03)
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- The Synthesis and Some Properties of the First Boron-Stabilized Alkenyl Carbanions
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Calculations indicate a high degree of stabilization of H2BC=CH2 and that it has an allene-type structure H2B=C=CH2.Routes to boron-stabilized alkenyl carbanions have been established for the first time, and alkylation and protonation studies are described.
- Pelter, Andrew,Smith, Keith,Parry, David E.,Jones, Kevin D.
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- Reaction of 1-alkenyl and 1-alkynyl derivatives of tin and mercury with hetero-centered radicals
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1-Alkenyl and 1-alkynyl derivatives of tin and mercury react with hetero-centered radicals such as RS., PhSe., PhSO2., or (EtO)2P(O). to undergo substitution of the metal atom in a free radical chain reaction involving addition-elimination. The hetero-centered radical can be formed in a chain propagation reaction by the attack of ClHg. or Bu3Sn. upon reagents such as RSSR, PhSeSO2Ph, PhSeSePh, or PhSO2Cl or mercurials such as Hg(SPh)2, Hg(SePh)2, Hg(O2SPh)2, or Hg[(O)P(OEt)2]2. In relative reactivity studies toward PhS., vinylmercury chlorides are somewhat more reactive than the analogous tri-n-butylstannanes. Tri-n-butyl(phenylethynyl)stannane is 300 times less reactive than its β-styrenyl analogue. Toward PhS., CH2=CHCH2SnBu3 is 3 times as reactive as CH2=CHSnBu3 but only 1/16 as reactive as (E)-PhCH= CHSnBu3. An explanation is advanced for the observations that PhSeSePh participates in a free radical chain substitution reaction with allylstannanes or 1-alkenylmercury chlorides but not with 1-alkenylstannanes although PhSSPh or (PhSe)2Hg react readily with 1-alkenylmercurials or -stannanes.
- Russell, Glen A.,Ngoviwatchai, Preecha,Tashtoush, Hasan,Hershberger, James
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p. 1414 - 1419
(2008/10/08)
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