- Bright blue phosphorescence from cationic bis-cyclometalated iridium(III) isocyanide complexes
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We report new bis-cyclometalated cationic iridium(III) complexes [(CN) 2Ir(CN-tert-Bu)2](CF3SO3) that have tert-butyl isocyanides as neutral auxiliary ligands and 2-phenylpyridine or 2-(4'- fluorophenyl)-R-pyridines (where R is 4-methoxy, 4-tert-butyl, or 5-trifluoromethyl) as CN ligands. The complexes are white or pale yellow solids that show irreversible reduction and oxidation processes and have a large electrochemical gap of 3.58-3.83 V. They emit blue or bluegreen phosphorescence in liquid/solid solutions from a cyclometalatingligand- centered excited state. Their emission spectra show vibronic structure with the highest-energy luminescence peak at 440-459 nm. The corresponding quantum yields and observed excitedstate lifetimes are up to 76% and 46 μs, respectively, and the calculated radiative lifetimes are in the range of 46-82 μs. In solution, the photophysical properties of the complexes are solvent-independent, and their emission color is tuned by variation of the substituents in the cyclometalating ligand. For most of the complexes, an emission color red shift occurs in going from solution to neat solids. However, the shift is minimal for the complexes with bulky tert-butyl or trifluoromethyl groups on the cyclometalating ligands that prevent aggregation. We report the first example of an iridium(III) isocyanide complex that emits blue phosphorescence not only in solution but also as a neat solid.
- Shavaleev, Nail M.,Monti, Filippo,Costa, Ruben D.,Scopelliti, Rosario,Bolink, Henk J.,Orti, Enrique,Accorsi, Gianluca,Armaroli, Nicola,Baranoff, Etienne,Graetzel, Michael,Nazeeruddin, Mohammad K.
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- BET INHIBITORS FOR MODULATING DUX4 EXPRESSION IN FSHD
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The present disclosure provides BET inhibitors of the formula: wherein the variables are defined herein, as well as pharmaceutical compositions thereof. The present disclosure also provides methods of treating a patient comprising administering a bromo- and extra-terminal (BET) domain inhibitor for the treatment of FSHD which modulates DUX4 expression. In some embodiments, the present methods comprise using one or more BET inhibitors as a therapeutic agent for the treatment of FSHD patients including patients who are being treated with one or more palliative treatments such as therapy and/or agents which lead to increased muscle mass.
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Page/Page column 203
(2020/07/14)
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- PYRROLIDINE OREXIN RECEPTOR ANTAGONISTS
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The present invention is directed to pyrrolidine compounds which are antagonists of orexin receptors. The present invention is also directed to uses of the compounds described herein in the potential treatment or prevention of neurological and psychiatric disorders and diseases in which orexin receptors are involved. The present invention is also directed to compositions comprising these compounds. The present invention is also directed to uses of these compositions in the potential prevention or treatment of such diseases in which orexin receptors are involved.
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Page/Page column 57
(2016/07/05)
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- Rhodium(I)-catalyzed direct carboxylation of arenes with CO2 via chelation-assisted C-H bond activation
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Rh-catalyzed direct carboxylation of unactivated aryl C-H bond under atmospheric pressure of carbon dioxide was realized via chelation-assisted C-H activation for the first time. Variously substituted and functionalized 2-arylpyridines and 1-arylpyrazoles underwent the carboxylation in the presence of the rhodium catalyst and a stoichiometric methylating reagent, AlMe 2(OMe), to give carboxylated products in good yields. The catalysis is proposed to consist of methylrhodium(I) species as the key intermediate, which undergoes C-H activation to afford rhodium(III), followed by reductive elimination of methane to give nucleophilic arylrhodium(I). This approach demonstrates promising application of C-H bond activation strategy in the field of carbon dioxide fixation.
- Mizuno, Hajime,Takaya, Jun,Iwasawa, Nobuharu
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supporting information; experimental part
p. 1251 - 1253
(2011/04/16)
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- COMPOUNDS AND METHODS OF USE
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Selected compounds are effective for prophylaxis and treatment of diseases, such as angiogenesis mediated diseases. The invention encompasses novel compounds, analogs, prodrugs and pharmaceutically acceptable salts thereof, pharmaceutical compositions and methods for prophylaxis and treatment of diseases and other maladies or conditions involving, cancer and the like. The subject invention also relates to processes for making such compounds as well as to intermediates useful in such processes.
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Page/Page column 111
(2010/11/27)
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- Concise total syntheses of variolin B and deoxyvariolin B
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The total synthesis of the marine alkaloid variolin B has been achieved in 8 steps and 17% overall yield, starting from commercially available 4-chloro-2-methylthiopyrimidine. The key reaction involves the tandem deoxygenation and cyclization of a triarylmethanol using a combination of triethylsilane and trifluoroacetic acid. In addition, the deoxygenated analogue was prepared in 6 steps and 23% overall yield, starting from the same starting material.
- Anderson, Regan J.,Hill, Jonathan B.,Morris, Jonathan C.
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p. 6204 - 6212
(2007/10/03)
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- Tetrabutylammonium salt induced denitration of nitropyridines: Synthesis of fluoro-, hydroxy-, and methoxypyridines
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(Chemical Equation Presented) An efficient method for the synthesis of fluoropyridines via the fluorodenitration reaction is reported. The reaction is mediated by tetrabutylammonium fluoride (TBAF) under mild conditions without undue regard to the presence of water. The fluorodenitration is general for 2- or 4-nitro-substituted pyridines, while 3-nitropyridines require attendant electron-withdrawing groups for the reaction to proceed efficiently. Nitropyridines also undergo hydroxy- and methoxydenitration under mild conditions in the presence of the corresponding tetrabutylammonium species.
- Kuduk, Scott D.,DiPardo, Robert M.,Bock, Mark G.
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p. 577 - 579
(2007/10/03)
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- Synthesis and biological activity of novel substituted pyridines and purines containing 2,4-thiazolidinedione
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A series of substituted pyridines and purines containing 2,4-thiazolidinedione were designed and synthesized from their corresponding pyridines and purines. These synthesized compounds (entry no. 6a-d, 12a-e, 18a-d, 23a-c) were evaluated for their effect on triglyceride accumulation in 3T3-L1 cells in vitro and their hypoglycemic and hypolipidemic activity in the genetically diabetic KKAy mice in vivo. On the basis of their biological activities, 5-(4-{2-[N-methyl-(5-phenyl-pyridin-2-yl)amino]ethoxy} benzyl)thiazolidine-2,4-dione (6d) was selected as a candidate for further pharmacological studies.
- Kim, Bok Young,Ahn, Joong Bok,Lee, Hong Woo,Kang, Sung Kwon,Lee, Jung Hwa,Shin, Jae Soo,Ahn, Soon Kil,Hong, Chung Il,Yoon, Seung Soo
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p. 433 - 447
(2007/10/03)
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- Stabilised 2,3-pyridyne reactive intermediates of exceptional dienophilicity
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The enhanced dienophilicity of 4-methoxy, 4-aryloxy and 4-thiophenoxy analogues 6-9 of 2,3-pyridyne (2) relative to 2 itself is reported. The regioselective lithiation of 4-alkoxy-(22, 23 and 25) and 4-thiophenoxy-2- chloropyridme (24) at low temperatures, followed by elimination of lithium chloride affords 4-alkoxy- and 4-thiophenoxypyridynes, which can be trapped in situ in a [4+2] cycloaddition reaction with furan to give endoxides 28-31 in moderate to good yields (25-58%). In contrast, precursors with a hydrogen (18) or methyl (12) substituent at C-4 give no evidence for pyridyne formation under these conditions. Attempts to generate 6-isopropoxy-2,3-pyridyne (10) from the low-temperature lithiation of 2-chloro-6-isopropoxypyridine were unsuccessful due to the instability of the 2-chloro-6-isopropoxy-5-lithiopyridine. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Connon, Stephen J.,Hegarty, Anthony F.
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p. 3477 - 3483
(2007/10/03)
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- N-(unsubstituted or substituted)-4-substituted-6-(unsubstituted or substituted)phenoxy-2-pyridinecarboxamides or thiocarboxamides, processes for producing the same, and herbicides
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N-(substituted or unsubstituted)-4-substituted-6-(substituted or unsubstituted) phenoxy-2-pyridine carboxamide or thiocarboxamide represented by the general formula (I) and a process for producing the compound. A herbicide containing as an effective ingredient N-(substituted or unsubstituted)-4-substituted-6-(substituted or unsubstituted) phenoxy-2-pyridine carboxamide or thiocarboxamide represented by the general formula (I).
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Referential example 2
(2010/01/30)
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- Diels-Alder cycloadditions of stabilised 2,3-pyridynes
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Investigation of electron donating substituents at C-4 on 2,3-pyridyne 1 stability has revealed a novel stabilisation of these reactive species by aryloxy and thiophenoxy groups leading to a relatively high yielding [4+2] cycloaddition between 4-(p-methoxyphenoxy)-2,3-pyridine and furan at low temperature.
- Connon, Stephen J.,Hegarty, Anthony F.
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p. 735 - 737
(2007/10/03)
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- Two new methods for 2,3-pyridyne formation
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The compounds 2-chloro-4-methoxypyridine and 4-methoxy-2-trifluoromethylsulfonyloxy-3-trimethylsilylpyridine were shown to be relatively efficient precursors for 4-methoxy-2,3-pyridyne as was evidenced by its trapping with furan, 2-methylfuran and 2-methoxyfuran. These findings constitute the first published report of the use of either directed-deprotonation or fluoride-induced elimination to prepare the reactive 2,3-pyridyne intermediate.
- Walters, Michael A.,Shay, John J.
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p. 7575 - 7578
(2007/10/02)
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