- C?N Cross-Coupling Reactions Under Mild Conditions Using Singlet Di-Radical Nickel(II)-Complexes as Catalyst: N-Arylation and Quinazoline Synthesis
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Herein we report a cost-effective synthetic approach for C?N cross-coupling reactions of a broad array of nitrogen nucleophiles and aryl halides under mild conditions. These reactions are catalyzed by an inexpensive, air-stable, earth-abundant and easy-to-prepare singlet di-radical nickel(II)-catalyst containing two antiferromagnetically coupled single-electron oxidized diiminosemiquinonato type ligands. This protocol provides an alternative method for C?N cross-coupling reactions avoiding nickel(0)/nickel(II) or nickel(I)/nickel(III) redox processes via cooperative participation of metal and ligand-centered redox events. Besides a wide range of N-arylation reactions, by judicious choice of aryl halides and nitrogen nucleophiles the synthesis of a variety of polysubstituted quinazolines has been achieved in moderate to good yields under relatively mild reaction conditions. Our catalyst has been found to be almost equally effective in quinazoline synthesis via C?N cross-coupling of (i) 2-bromobenzylamine with benzamide, and (ii) 2-bromobenzylbromide with amidine. Control experiments and DFT studies were performed to improve the understanding of the cooperative participation of ligand and metal (nickel)-centered redox events during oxidative addition/reductive elimination processes of the catalytic cycle and to shed light on the plausible mechanistic pathway of the C?N cross-coupling reactions. (Figure presented.).
- Sikari, Rina,Sinha, Suman,Chakraborty, Gargi,Das, Siuli,van Leest, Nicolaas Petrus,Paul, Nanda D.
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supporting information
p. 4342 - 4353
(2019/08/21)
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- ISOINDOLINE-1-ONE DERIVATIVES AS CHOLINERGIC MUSCARINIC M1 RECEPTOR POSITIVE ALLOESTERIC MODULATOR ACTIVITY FOR THE TREATMENT OF ALZHEIMERS DISEASE
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The present invention provides a compound having a cholinergic muscarinic M1 receptor positive allosteric modulator activity and useful as an agent for the prophylaxis or treatment of Alzheimer's disease, schizophrenia, pain, sleep disorder, Parkinson's disease dementia, dementia with Lewy bodies, and the like. The present invention relates to a compound represented by the formula (I) or a salt thereof. (I) wherein each symbol is as described in the specification, or a salt thereof.
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Paragraph 0386
(2015/11/10)
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- HIGH-SENSITIVITY NEAR-INFRARED PHOSPHORESCENT IRIDIUM COMPLEX FOR MEASURING OXYGEN CONCENTRATION IN CELL/TISSUE
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PROBLEM TO BE SOLVED: To provide a compound with a long phosphorescence lifetime which can efficiently measure the oxygen concentration in a cell, tissue or the like. SOLUTION: The oxygen concentration is measured using a compound represented by the gener
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Paragraph 0024
(2018/12/01)
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- Pd-catalyzed aldehyde to ester conversion: A hydrogen transfer approach
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Aliphatic and aromatic aldehydes are successfully converted into their corresponding esters using Pd(OAc)2 and XPhos. This approach utilizes a hydrogen transfer protocol: concomitant reduction of acetone to isopropanol provides an inexpensive and sustainable approach that mitigates the need for other oxidants.
- Tschaen, Brittany A.,Schmink, Jason R.,Molander, Gary A.
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supporting information
p. 500 - 503
(2013/04/11)
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- Iron complex-catalyzed N-arylation of pyrazoles under aqueous medium
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Commercially available FeCl3·6H2O with conformationally rigid diamine ligand is a highly effective catalyst for N-arylation of pyrazoles using aryl and heteroaryl iodides. It is notable to show that this complex is tolerable under aqueous medium and particularly the whole reaction utilizes water as the sole solvent without any additional organic co-solvents and surfactants. Attempted study using other nitrogen nucleophiles is described. This newly developed system provides an alternative protocol to Cu- and Pd-catalyzed N-arylation reactions.
- Lee, Hang Wai,Chan, Albert S.C.,Kwong, Fuk Yee
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experimental part
p. 5868 - 5871
(2010/01/11)
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- Selective androgen receptor modulators
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This invention provides compounds of formulas I, Ia, Ib, Ic, Id, Ie, and or salts thereof, pharmaceutical compositions comprising a compound of formulas I, Ia, Ib, Ic, Id, Ie, and a pharmaceutically acceptable excipient, methods of modulating the androgen receptor, methods of treating diseases beneficially treated by an androgen receptor modulator (e.g., sarcopenia, prostate cancer, contraception, type 2 diabetes related disorders or diseases, anemia, depression, and renal disease) and processes for making compounds of formulas I, Ia, Ib, Ic, Id, Ie, and intermediates useful in the preparation of same.
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Page/Page column 100-101
(2009/10/18)
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- IRON-COPPER CO-CATALYZED PROCESS FOR CARBON-CARBON OR CARBON-HETEROATOM BONDING
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The present invention relates to a process for creating a Carbon-Carbon bond (C-C) or a Carbon-Heteroatom bond (C -HE) by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) that can substitute for the leaving group, creating a C-C or C-HE bond, wherein the reaction takes place in the presence of an effective quantity of a catalytic system comprising iron and copper.
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Page/Page column 41-42
(2008/06/13)
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- Efficient iron/copper co-catalyzed arylation of nitrogen nucleophiles
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(Chemical Equation Presented) An ideal pair: Various substituted aryl halides react under mild conditions with nitrogen heterocycles in the presence of catalytic amounts of [Fe(acac)3] (acac = acetylacetonate) and copper salts to give the corresponding cross-coupling products in high yields (see scheme). This cheap and environmentally friendly cocatalyst system is the first example of cooperative Fe/Cu catalysis in this type of N-C bond formation.
- Taillefer, Marc,Xia, Ning,Ouali, Armelle
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p. 934 - 936
(2008/02/01)
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- Ligand-free copper-catalyzed N-arylation of nitrogen nucleophiles
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Versatile, simple and inexpensive ligand-free, copper-catalyzed N-arylations of sulfoximines and nitrogen-containing heterocycles have been developed affording N-arylated products in high yields.
- Correa, Arkaitz,Bolm, Carsten
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p. 2673 - 2676
(2008/09/19)
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- Iron-catalyzed N-arylation of nitrogen nucleophiles
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(Chemical Equation Presented) Easy does it! A simple procedure for the N-arylation of nitrogen-containing heterocycles and primary amides relies on a catalyst formed in situ from inexpensive and environmentally benign FeCl 3 and a diamine ligand. The cross-coupling reaction with aryl halides provides N-arylated compounds in high yields (see scheme; R = H, Cl, Me, OMe, CO2Et, F, CF3).
- Correa, Arkaitz,Bolm, Carsten
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p. 8862 - 8865
(2008/09/19)
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- FIBROSIS INHIBITOR
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Medicament being useful as a fibrosis inhibitor for organs or tissues, which comprises a compound of the formula (I): wherein Ring Z is optionally substituted pyrrole ring, etc.; W2 is -CO-, -SO2-, optionally substituted C1-C4 alkylene, etc.; Ar2 is optionally substituted aryl, etc.; W1 and Ar1 mean the following (1) and (2):(1) W1 is optionally substituted C1-C4 alkylene, etc.; Ar1 is optionally substituted bicyclic heteroaryl having 1 to 4 nitrogen atoms as ring-forming atoms:(2) W1 is optionally substituted C2-C5 alkylene, optionally substituted C2-C5 alkenylene, etc.; and Ar1 is aryl or monocyclic heteroaryl, which is substituted by carboxyl, alkoxycarbonyl, etc. at the ortho- or meta-position thereof with respect to the binding position of W1, or a pharmaceutically acceptable salt thereof.
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- Pyrrole derivatives
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Pyrrole derivatives represented by the following formula: wherein Ring Z is an optionally substituted pyrrole ring, etc.; W2 is —CO—, —SO2—, an optionally substituted C1-C4 alkylene, etc.; Ar2 is an optionally substituted aryl, etc.; W2 and Ar1 mean the following (1) and (2): (1) W1 is an optionally substituted C1-C4 alkylene, etc.; Ar1 is an optionally substituted bicyclic heteroaryl having 1 to 4 nitrogen atoms as ring-forming atoms: (2) W1 is an optionally substituted C2-C5 alkylene, an optionally substituted C2-C5 alkenylene, etc.; and Ar1 is an aryl or monocyclic heteroaryl, which are substituted by carboxyl, an alkoxycarbonyl, etc. at the ortho- or meta-position thereof with respect to the binding position of W1, or a pharmaceutically acceptable salt thereof These compounds are useful as medicaments such as a fibrosis inhibitor for organs or tissues.
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- Aromatic hydrazides as specific inhibitors of bovine serum amine oxidase
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New hydrazides were synthesized in search for specific inhibitors of bovine serum amine oxidase: a series of benzoic and phenylacetic acid hydrazides containing the 1H-imidazol-1-yl or the 1H-imidazol-1-ylmethyl group as (o,m,p)-substituent in the phenyl ring; an analogous series of p-substituted phenylhydrazides with 5 or 6-membered heterocyclic ring as substituent, and a series of similar phenylpropionic hydrazides. The longer and more flexible phenylacetic hydrazides, and to a somewhat lesser extent the phenylpropionic ones, were better specific inhibitors of bovine serum amine oxidase than the benzoic hydrazides, which were also bound by the enzyme with high affinity, but at a slow rate. Derivatives with p- and m-substituents were more reactive than the o-substituted ones. The chemical nature of the substituent was less important than its position in the phenyl ring and the presence of methylene spacers. These data point to the presence of a hydrophobic site at short distance from the protein carbonyl cofactor, so that simultaneous interaction of the 2 ends of the inhibitor molecule can occur at the 2 sites. The presence of the hydrophobic site was confirmed by the capability of some molecule deprived of the hydrazidic group to act as mild inhibitors. All hydrazides were less reactive by 2-3 orders of magnitude towards pig kidney diamine oxidase and FAD-dependent monoamine oxidase from rat brain mitochondria, while the other compounds showed similar inhibition power against all proteins. The specificity for the bovine enzyme seems therefore to be related to the concerted action of the 2 moieties of the inhibitor molecule.
- Artico,Silvestri,Stefancich,Avigliano,Di Giulio,Maccarrone,Agostinelli,Mondovi,Morpurgo
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p. 219 - 228
(2007/10/02)
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