- 2-(4′-Pyridyl-N-oxide)-Substituted Hemithioindigos as Photoresponsive Guests for a Super Aryl-Extended Calix[4]pyrrole Receptor
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We report the synthesis of two 2-(4′-pyridyl-N-oxide)-substituted hemithioindigos (HTIs). We probed their photoisomerization by using UV/Vis and 1H NMR spectroscopy techniques. Light irradiation at λ=450 nm provoked the isomerization of the HTI Z isomer to the E counterpart to a large extent (≈80 % at the photostationary state). 1H NMR titration experiments revealed the formation of thermodynamically and kinetically stable 1:1 inclusion complexes of the (Z)-HTI isomers with a super aryl-extended host (association constant>104 m?1). Photoirradiation at λ=450 nm of the inclusion complexes induced the isomerization of the bound HTI N-oxide to afford the (E)-HTI?calix[4]pyrrole complex. We determined accurate association constant values for the 1:1 inclusion complexes of the (Z)- and (E)-HTI isomers by using isothermal titration calorimetry experiments. The results showed that the stability constants of the (E)-HTI complexes were 2.2–2.8-fold lower than those of the (Z)-HTI counterparts, which explains the lack of light-induced release of the former to the bulk solution.
- Moncelsi, Giulia,Escobar, Luis,Dube, Henry,Ballester, Pablo
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- From Pyridine- N-oxides to 2-Functionalized Pyridines through Pyridyl Phosphonium Salts: An Umpolung Strategy
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The reactions of pyridine-N-oxides with Ph3P under the developed conditions provide an unprecedented route to (pyridine-2-yl)phosphonium salts. Upon activation with DABCO, these salts readily serve as functionalized 2-pyridyl nucleophile equivalents. This umpolung strategy allows for the selective C2 functionalization of the pyridine ring with electrophiles, avoiding the generation and use of unstable organometallic reagents. The protocol operates at ambient temperature and tolerates sensitive functional groups, enabling the synthesis of otherwise challenging compounds.
- Bugaenko, Dmitry I.,Yurovskaya, Marina A.,Karchava, Alexander V.
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supporting information
p. 6099 - 6104
(2021/08/03)
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- Reaction of Pyridine-N-Oxides with Tertiary sp2-N-Nucleophiles: An Efficient Synthesis of Precursors for N-(Pyrid-2-yl)-Substituted N-Heterocyclic Carbenes
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N-(Pyrid-2-yl)-substituted azolium and pyridinium salts, precursors for hybrid NHC-containing ligands, were obtained with excellent regioselectivity, employing a deoxygenative CH-functionalization of pyridine-N-oxides with substituted imidazoles, thiazoles, and pyridine. Unlike the traditional SNAr-based methods, this approach provides high yields for substrates bearing substituents of different electronic nature. The utility of azolium and pyridinium salts thus prepared was also highlighted by the synthesis of pyridyl-substituted imidazolyl-2-thione, benzodiazepine as well as 2-aminopyridines.
- Bugaenko, Dmitry I.,Karchava, Alexander V.,Yurovskaya, Marina A.
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supporting information
p. 5777 - 5782
(2020/12/01)
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- MANUFACTURING METHOD OF OPTICAL ACTIVE SECONDARY ALCOHOL
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PROBLEM TO BE SOLVED: To provide a method for manufacturing optical active secondary alcohol with high optical purity by hydrogenating a substrate carbonyl compound using a ruthenium complex with a specific optical active diphosphine compound and an amine compound of which synthesis is easy as ligands as a catalyst. SOLUTION: The manufacturing method of optical active secondary alcohol including reacting a substrate carbonyl compound (excluding 3-quinuclidinone, a 3-quinuclidinone derivative having a substituent, and ketone having an aromatic hydrocarbon group and a heterocycle) with hydrogen and/or a hydrogen-donating compound in a presence of a ruthenium complex selected from a compound represented by the following general formula (1) RuXYAB (1) [X and Y are same or different, represent a hydrogen atom or an anionic group, A represents optical active diphosphine represented by the general formula (2), and B represents an amine compound represented by the following general formula (3)]. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPO&INPIT
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Paragraph 0094; 0098
(2019/03/20)
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- Base free regioselective synthesis of α-triazolylazine derivatives
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A regioselective α-heteroarylation followed by deoxygenation towards the synthesis of variety of azine triazole from simple azine N-oxides derivatives and N-tosyl-1,2,3-triazoles has been described. The reaction is metal free and base free with shorter reaction time, high yields and a broad substrate scope.
- Harisha, Mysore Bhyrappa,Nagaraj, Muthupandi,Muthusubramanian, Shanmugam,Bhuvanesh, Nattamai
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p. 58118 - 58124
(2016/07/06)
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- PROCESS FOR PRODUCING OPTICALLY ACTIVE SECONDARY ALCOHOL
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[Object] The object of this invention is to provide a method for producing an optically active secondary alcohol at a high optical purity by hydrogenating a substrate carbonyl compound at a high efficiency using as a catalyst a ruthenium complex bearing as a ligand certain optically active diphosphine compound and a readily synthesized amine compound. [Solution] The method of producing an optically active secondary alcohol according to the present invention is characterized in that a substrate carbonyl compound (provided that 3-quinuclidinone, 3-quinuclidinone derivative having a substituent, and a ketone having an aromatic hydrocarbon group and a heterocycle are excluded) is reacted with hydrogen and/or a hydrogen donating compound in the presence of a ruthenium complex selected from the compounds expressed by following general formula (1) RuXYAB (1) [in the general formula (1), X and Y are the same or different from each other and denote a hydrogen atom or an anionic group, A denotes an optically active diphosphine expressed by the general formula (2), B denotes an amine compound expressed by following general formula (3)].
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Paragraph 0146; 0149
(2015/02/19)
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- Structure activity relationship of pyridoxazinone substituted RHS analogs of oxabicyclooctane-linked 1,5-naphthyridinyl novel bacterial topoisomerase inhibitors as broad-spectrum antibacterial agents (Part-6)
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Abstract Oxabicyclooctane linked 1,5-naphthyridinyl-pyridoxazinones are novel broad-spectrum bacterial topoisomerase inhibitors (NBTIs) targeting bacterial DNA gyrase and topoisomerase IV at a site different than quinolones. Due to lack of cross-resistance to known antibiotics they present excellent opportunity to combat drug-resistant bacteria. A structure activity relationship of the pyridoxazinone moiety is described in this Letter. Chemical synthesis and activities of NBTIs with substitutions at C-3, C-4 and C-7 of the pyridoxazinone moiety with halogens, alkyl groups and methoxy group has been described. In addition, substitutions of the linker NH proton and its transformation into amide analogs of AM-8085 and AM-8191 have been reported. Fluoro, chloro, and methyl groups at C-3 of the pyridoxazinone moiety retained the potency and spectrum. In addition, a C-3 fluoro analog showed 4-fold better oral efficacy (ED50 3.9 mg/kg) as compared to the parent AM-8085 in a murine bacteremia model of infection of Staphylococcus aureus. Even modest polarity (e.g., methoxy) is not tolerated at C-3 of the pyridoxazinone unit. The basicity and NH group of the linker is important for the activity when CH2 is at the linker position-8. However, amides (with linker position-8 ketone) with a position-7 NH or N-methyl group retained potency and spectrum suggesting that neither basicity nor hydrogen-donor properties of the linker amide NH is essential for the activity. This would suggest likely an altered binding mode of the linker position-7,8 amide containing compounds. The amides showed highly improved hERG (functional IC50 >30 μM) profile.
- Singh, Sheo B.,Kaelin, David E.,Wu, Jin,Miesel, Lynn,Tan, Christopher M.,Meinke, Peter T.,Olsen, David B.,Lagrutta, Armando,Wei, Changqing,Liao, Yonggang,Peng, Xuanjia,Wang, Xiu,Fukuda, Hideyuki,Kishii, Ryuta,Takei, Masaya,Yajima, Masanobu,Shibue, Taku,Shibata, Takeshi,Ohata, Kohei,Nishimura, Akinori,Fukuda, Yasumichi
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p. 3636 - 3643
(2015/08/06)
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- Insights into the mechanistic and synthetic aspects of the Mo/P-catalyzed oxidation of N-heterocycles
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A Mo/P catalytic system for an efficient gram-scale oxidation of a variety of nitrogen heterocycles to N-oxides with hydrogen peroxide as terminal oxidant has been investigated. Combined spectroscopic and crystallographic studies point to the tetranuclear Mo4P peroxo complex as one of the active catalytic species present in the solution. Based on this finding an optimized catalytic system has been developed. The utility and chemoselectivity of the catalytic system has been demonstrated by the synthesis of over 20 heterocyclic N-oxides.
- Larionov, Oleg V.,Stephens, David,Mfuh, Adelphe M.,Arman, Hadi D.,Naumova, Anastasia S.,Chavez, Gabriel,Skenderi, Behije
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p. 3026 - 3036
(2014/05/06)
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- Synthesis of two potential heterocyclic amine food mutagens
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(Chemical Equation Presented) The syntheses of two potential food mutagens formed during cooking, 2-amino-3,6,7-trimethyl-3H-imidazo[4,5-b]pyridine (1) and 2-amino-3,6,7-trimethyl-3H-imidazo[4,5-c]pyridine (2), are described.
- Tanga, Mary J.,Kozocas, Joseph A.,Tochimoto, Todd K.
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p. 661 - 665
(2008/09/21)
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- MODULATORS OF CFTR
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Compounds of the present invention, and pharmaceutically acceptable compositions thereof, are useful as modulators of ATP-Binding Cassette ("ABC") transporters or fragments thereof, including Cystic Fibrosis Transmembrane Conductance Regulator ("CFTR"). The present invention also relates to methods of treating CFTR mediated diseases using compounds of the present invention.
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Page/Page column 87
(2009/01/20)
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- PYRIDINE DERIVATIVES AND THEIR USE AS MEDICAMENTS FOR TREATING DISEASES RELATED TO MCH RECEPTOR
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The present invention encompasses novel substituted pyridine compounds of Formula (I), which act as MCH receptor antagonists. These compositions and pharmaceutical compositions thereof are useful in the prophylaxis or treatment of improving memory function, sleeping and arousal, anxiety, depression, mood disorders, seizure, obesity, diabetes, appetite and eating disorders, cardiovascular disease, hypertension, dyslipidemia, myocardial infarction, binge eating disorders including bulimia, anorexia, mental disorders including manic depression, schizophrenia, delirium, dementia, stress, cognitive disorders, attention deficit disorder, substance abuse disorders and dyskinesias including Parkinson's disease, epilepsy, and addiction.
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Page/Page column 96
(2010/10/20)
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- On the preparation of amine N-oxides by using dioxiranes
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The reaction of heterocyclic aromatic amines, anilines and tertiary amines with dimethyldioxirane (DMD) was examined. Treatment of heterocyclic aromatic amines and anilines with a slight excess of DMD at 0°C afforded the corresponding N-oxides in quantitative conversion yields. In addition, the oxidation was chemoselective in the presence of carbon-carbon double bonds. On the other hand, most of the tertiary amines assayed did afford also quantitative yields of the corresponding N. oxides, although reaction conditions, in particular regarding the amount of DMD required, depended on each substrate. Additional studies carried out on selected substrates suggested that certain N-oxides derived from tertiary amines deactivate DMD.
- Ferrer, Marta,Sanchez-Baeza, Francisco,Messeguer, Angel
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p. 15877 - 15888
(2007/10/03)
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- Carbapenem antibiotics
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Disclosed are novel carbapenem derivatives characterized by a 2-substituent of the formula STR1 in which A represents a C1 -C6 straight or branched chain alkylene group; R5 represents an optionally substituted aliphatic, cycloaliphatic, cycloaliphatic-aliphatic, aryl, araliphatic, heteroaryl, heteroaraliphatic, heterocyclyl or heterocyclyl-aliphatic radial and STR2 represents a nitrogen-containing aromatic heterocycle attached to the alkylene group A at a ring carbon atom and quaternized by substituent R5. Such derivatives are useful as potent antibacterial agents.
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