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A copper-based metal-organic framework as an efficient and reusable heterogeneous catalyst for ullmann and goldberg type C-N coupling reactions

A highly porous metal-organic framework (Cu-TDPAT), constructed from a paddle-wheel type dinuclear copper cluster and 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (H6TDPAT), has been tested in Ullmann and Goldberg type C-N coupling reactions of a wide range of primary and secondary amines with halobenzenes, affording the corresponding N-arylation compounds in moderate to excellent yields. The Cu-TDPAT catalyst could be easily separated from the reaction mixtures by simple filtration, and could be reused at least five times without any significant degradation in catalytic activity.

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Isoxazole – Wikipedia,
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Supramolecular chemistry and self-organization: A veritable playground for catalysis

The directed assembly of molecular building blocks into discrete supermolecules or extended supramolecular networks through noncovalent intermolecular interactions is an ongoing challenge in chemistry. This challenge may be overcome by establishing a hierarchy of intermolecular interactions that, in turn, may facilitate the edification of supramolecular assemblies. As noncovalent interactions can be used to accelerate the reaction rates and/or to increase their selectivity, the development of efficient and practical catalytic systems, using supramolecular chemistry, has been achieved during the last few decades. However, between discrete and extended supramolecular assemblies, the newly developed ?colloidal tectonics? concept allows us to link the molecular and macroscopic scales through the structured engineering of colloidal structures that can be applied to the design of predictable, versatile, and switchable catalytic systems. The main cutting-edge strategies involving supramolecular chemistry and self-organization in catalysis will be discussed and compared in this review.

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Copper-catalyzed N- and O-alkylation of amines and phenols using alkylborane reagents

By the reaction of amines with alkylborane reagents in the presence of a catalytic amount of copper(II) acetate Cu(OAc)2 and di-tert-butyl peroxide, a cross-coupling reaction proceeded and alkylated amines were obtained in good to excellent yields. Phenols are also applicable for this reaction, and the corresponding alkyl aryl ethers were produced.

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Electronic effect of substituents on anilines favors 1,4-addition to: Trans -beta-nitrostyrenes: Access to N -substituted 3-arylindoles and 3-arylindoles

A simple and an efficient method for the regioselective synthesis of N-alkyl/aryl/H 3-arylindole derivatives from N-substituted anilines and trans-beta-nitrostyrenes has been described using 10 mol% of bismuth(iii) triflate as a catalyst in acetonitrile at 80 C. The present protocol profits from the formation of new C-C and C-N bonds, broad substrate scope and moderate to good yields.

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Top Picks: new discover of Ethyl 5-(4-methoxyphenyl)isoxazole-3-carboxylate

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Novel 1,3-dipropyl-8-(1-heteroarylmethyl-1H-pyrazol-4-yl)-xanthine derivatives as high affinity and selective A2B adenosine receptor antagonists

A series of new 1,3-dipropyl-8-(1-heteroarylmethyl-1H-pyrazol-4-yl)- xanthine derivatives as A2B-AdoR antagonists have been synthesized and evaluated for their binding affinities for the A2B, A 1, A2A, and A3-AdoRs. 8-(1-((3-phenyl-1,2,4- oxadiazol-5-yl)methyl)-1H-pyrazol-4-yl)-1,3-dipropyl-1H-purine-2,6(3H,7H)-dione (4) displayed high affinity (Ki = 1 nM) and selectivity for the A2B-AdoR versus A1, A2A, and A 3-AdoRs (A1/A2B, A2A/A2B, and A3/A2B selectivity ratios of 370, 1100, and 480, respectively). The synthesis and SAR of this novel class of compounds are presented herein.

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Amidines. Part 30. Influence of Substitution at Amino Nitrogen Atom on pKa Values of N2-Phenylacetamidines and N2-Phenylamidines

A series of N2-phenylacetamidines and N2-phenylformamidines (22 compounds) containing variable substituents at amino nitrogen atom have been synthesized, and their pKa values in 95.6percent ethanol (azeotrope) measured.The pKa values obtained for N1-methyl-N1,N2-diphenylacetamidines were correlated with Hammett type constants.Applicability of various ? values is discussed and it is shown that for substituents on the phenyl ring at amino nitrogen atom ?0 values should be used.It is also shown that the pKa values of amidines correlate well with the pKa values of corresponding secondary amines, and that this correlation can serve the prediction of the pKa of amidine. Comparison of the correlations obtained for studied acetamidines and formamidines indicates that sensitivity of the amidino group to substitution at the amino nitrogen atom depends to a certain degree on the substituent at the functional carbon atom.

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An efficient method for the N-formylation of amines under catalyst- and additive-free conditions

A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.

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Convenient Reductive Methylation of Amines with Carbonates at Room Temperature

Methylation of amines is a fundamental and commonly used reaction in organic synthesis. Many methods are known including various reductive methylations using formaldehyde, formic acid, or carbon dioxide in the presence of reductants. However, several of these methods suffer from limited substrate scope and chemoselectivity because of the different nucleophilicities of substrates. In this respect, the combination of carbonates and hydrosilanes is a valuable methylation source in the presence of Pt-based catalysts. This highly tunable method allows for methylation of both aromatic and aliphatic amines, and chemoselective methylation of aminoalcohols and diamines. Notably, the in situ-formed catalyst can also be used for the reduction of carbonates to methanol at room temperature. Mechanistic insights on intermediates formed during the reaction pathway were obtained by using ESI mass spectrometry.

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Cyclopenta[d]pyrimidines And Substituted Cyclopenta[d]pyrimidines As Antitubulin and Microtubule Targeting Agents, Monocyclic Pyrimidines As Tubulin Inhibitors, And Pyrrolopyrimidines As Targeted Antifolates And Tubulin and Multiple Receptor Tyrosine Kinase Inhibition And Antitumor Agents

The present invention provides a compound of Formula I, and salts thereof, and a pharmaceutical composition comprising a compound of Formula I: wherein R1 is selected from the group consisting of and R2 is an alkyl group having from one to ten carbon atoms, or wherein R2 is selected from the group consisting of R1 is an alkyl group having from one to ten carbon atoms; and R is H, or an alkyl group having from one to ten carbon atoms, and R3 is H, an alkyl group having from one to ten carbon atoms, or a halogen. Preferably the compound of Formula V includes wherein R3 is a halogen, and most preferably wherein the halogen is chlorine. Methods of treating a patient with cancer with these compounds are also provided.

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Carbon Dioxide Reduction to Methylamines under Metal-Free Conditions

The first metal-free catalysts are reported for the methylation of amines with carbon dioxide. Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new methodology enables the methylation of N-H bonds in a wide variety of amines, including secondary amines, with increased chemoselectivity. Organocatalysis: Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new method makes possible the methylation of N-H bonds in a wide variety of amines, including secondary amines (see picture), with increased chemoselectivity.

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Reference:
Isoxazole – Wikipedia,
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