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Related Products of 108-47-4, The transformation of simple hydrocarbons into more complex and valuable products via catalytic C–H bond functionalisation has revolutionised modern synthetic chemistry. 108-47-4, Name is 2,4-Dimethylpyridine,introducing its new discovery.

Bispidines (3,7-diazabicyclo[3.3.1]nonanes) as very rigid and highly preorganized ligands find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by 64Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper(II) complexes of 15 tetradentate bispidines can be varied by substitution of the pyridine rings (variation of the redox potential over ca. 450 mV and of the complex stability over approximately 10 log units). It is also shown that these variations are predictable by the pKa values of the pyridine groups as well as by the Hammett parameters of the substituents, and the density functional theory based energy decomposition analysis also allows one to accurately predict the redox potentials and concomitant complex stability. It is shown that the main contribution emerges from the electrostatic interaction energy, and the partial charges of the pyridine donor groups therefore also correlate with the redox potentials.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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An ambient and high-pressure stopped-flow kinetic study of the halogen-bridge cleavage reaction in the pallada- and platina-cycles <2> (M = Pd or Pt; R = H, 4-MeO, 5-Me or 5-F; X = Cl or I) by a series of substituted pyridines in chloroform as solvent revealed that it is a fast, associatively driven second-order process, with strong steric rather than electronic demands.Substituent effects and activation parameters (DeltaH(excit.),DeltaS(excit.) and DeltaV(excit.)) were in full accord with the proposed associative mechanism.The Pd dimers transformed into N,N-trans monomers of the type (py = pyridine).In contrast, the Pt counterparts afford N,N-cis species under the same conditions.The geometry of the N,N-cis complex X(py)>, as well as of the N,N-trans platinacycle Cl(py)>, has been confirmed by X-ray crystallography.The most striking structural differences in the N,N-cis and N,N-trans related platinacycles are the Pt-Cl and Pt-N(py) bond distances <2.300(1) and 2.408(5), 2.138(4) and 2.02(1) Angstroem, respectively>.The crystal structure of trans-<(n-Bu3P)IPd(mu-I)2PdI(P-n-Bu3)> has also been determined and used to account for its similar reactivity to <2> in the bridge-splitting reaction.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Awesome Chemistry Experiments For 3,4-Di(1H-indol-3-yl)-1H-pyrrole-2,5-dione

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As part of a program aimed at designing more potent and selective antagonists of the antidiuretic responses to arginine-vasopressin (AVP), the authors substituted O-alkyl-D-tyrosine (where alkyl=methyl, ethyl, isopropyl, or n-propyl) at position 2 in our eight previously reported O-alkyl-L-tyrosine antagonists of antidiuretic and vasopressor responses to AVP. The authors also substituted D-tyrosine for L-tyrosine in two vasopressor antagonists with weak antidiuretic agonistic activity, [1-(beta-mercapto-beta,beta-cyclopentamethylenepropionic acid),4-valine,8-D-arginine]vasopressin [d(CH2)5VDAVP] and its L-arginine isomer [d(CH2)5VAVP]. The ten analogues, synthesized by the solid-phase method, are as follows: 1) d(CH2)5-D-Tyr(Me)VDAVP; 2) d(CH2)5-D-Tyr(Et)VDAVP; 3) d(CH2)5-D-Tyr(i-Pr)VDAVP; 4) d(CH2)5-D-Tyr(n-Pr)VDAVP; 5) d(CH2)5-D-Tyr(Me)VAVP; 6) d(CH2)5-D-Tyr(Et)VAVP; 7) d(CH2)5-D-Tyr(n-Pr)VAVP; 8) d(CH2)5-D-Tyr(i-Pr)VAVP; 9) d(CH2)5-D-TyrVDAVP; 10) d(CH2)5-D-TyrVAVP. These analogues were tested for agonistic and antagonistic activities in rat antidiuretic and rat vasopressor systems. All ten D-tyrosine analogues possess transient weak antidiuretic activities (0.004-0.05 U/mg). Subsequent doses of AVP are reversibly antagonized for 1-3 h, depending on the dose of the antagonist. They exhibit the following antidiuretic pA2 values: 1) 7.19±0.11; 2) 7.59±0.04; 3) 7.51±0.06; 4) 7.60±0.05; 5) 7.77±0.07; 6) 7.81±0.07; 7) 7.66±0.11; 8) 7.61±0.06; 9) 7.03±0.05; 10) 7.51±0.08. They are all effective antagonists of vasopressor responses to AVP. Analogues 1-8 are two to ten times more potent than their respective O-alkyl-L-tyrosine isomers as antidiuretic antagonists. Since the vasopressor potencies of the O-alkyl-L-tyrosine analogues have either diminished or remained virtually unchanged, these analogues exhibit a selective increase in their antiantidiuretic/antivasopressor ratios with respect to their respective O-alkyl-L-tyrosine analogues. The finding that the substitution of an unalkylated D-tyrosine for L-tyrosine in d(CH2)5VDAVP and d(CH2)5VAVP converts these weak antidiuretic agonists into potent antagonists of antidiuretic responses to AVP is highly significant, especially in view of the relative ease of synthesis and much higher yields of unalkylated vs. alkylated tyrosine analogues. These ten new analogues are potentially useful as pharmacological tools and as therapeutic agents. The findings presented here have also obvious potential for the design of even more potent and selective antidiuretic antagonists.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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A diastereomer complex obtained via a process for the separation of enantiomers is disclosed, wherein separation can be rapidly effected such that enantiomers are obtained with high e.e. values. The process pets the separation of mixtures of enantiomers in which more than one resolving agent is used, of which at least one resolving agent is optically active, and which yields a diastereomer complex containing at least two resolving agents in optically active form. The process provides for, inter alia, a diastereomer complex having at least three compounds of which at least two compounds are resolving agents in optically active form, and at least one compound is an onantiomer in optically active form. Also provided is a diastereomer complex having at least three compounds of which at lea one compound is a resolving agent in optically active form, and at least two compounds which are enantiomers in optically active form.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Stereocontrolled syntheses of hydroxyethylene dipeptide isostere and aminoalkyl epoxides for hydroxyethylamine isosteres are described. The stereochemistry of both stereogenic centers of the aminoalkyl epoxides 10 and 15 as well as they gamma-lactone 17 was assembled by our recently developed highly selective ester-derived titanium enolate aldol reactions. The Ti- enolate of 6 reacted with (benzyloxy)acetaldehyde and cinnamaldehyde to provide the syn-aldol product 7 and anti-aldol product 12, respectively. Removal of the chiral template followed by Curtius rearrangement of the resulting acid provided the desired amine functionality. The present syntheses represent practical and enantioselective entry to a range of other dipeptide isosteres, which are not limited to amino acid derived substituents.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The present invention refers to the first one-pot synthesis of squaramides. The one-pot synthesis of squaramides described herein is an easy and straightforward procedure to obtain squaramide derivatives which saves energy, avoids time consuming purification steps, reduces costs and provides better yields as compared with those squaramides obtained through the traditional “stop-and-go” approach. Moreover, the authors of the present invention herein demonstrate the efficiency of this one-pot process with the synthesis of three biologically active structures, improving in most of the cases the results of the previous stepwise syntheses.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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A process for making a clinically efficacious HIV protease inhibitor Compound J eliminates one step in its synthesis, by an improved, alternative synthesis of the 2(S)-4-picolyl-2-piperazine-t-butyl-carboxamide intermediate.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The present invention relates to derivatized cyclofructan compounds, compositions comprising derivatized cyclofructan compounds, and methods of using compositions comprising derivatized cyclofructan compounds for chromatographic separations of chemical species, including enantiomers. Said compositions may comprise a solid support and/or polymers comprising derivatized cyclofructan compounds.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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While the job of a research scientist varies, most chemistry careers in research are based in laboratories, where research is conducted by teams following scientific methods and standards. Electric Literature of 108-47-4, Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. In an article,Which mentioned a new discovery about 108-47-4

gamma-Ray irradiation of a binary solution consisting of pyridine and methanol caused almost no reaction of pyridine.However, the addition of a catalytic amount of nickel nitrate to this binary solution induced the alpha-methylation of pyridine in good yield upon gamma-ray irradiation at room temperature either in air or in vacuo.This alpha-methylation gave alpha-picoline as a major product.The yield of alpha-picoline increased with increase in the irradiation time at the initial stage of the reaction, reached a maximum (27.8percent) at an irradiation duration of between 8 and 10h, and then decreased progressively at greater irradiation times.In addition, the yield of alpha-picoline at a given irradiation time showed a tendency to increase with increasing amount of the nickel nitrate catalyst or with increasing fraction of methanol in the starting solution. gamma-Ray irradiation in the presence of nickel nitrate was also found to induce the catalytic alpha-methylation of gamma-picoline with methanol at room temperature either in air or in vacuo, giving 2,4-lutidine as a major product in a maximum yield of 8.3percent.Further, the demethylation reaction of alpha-picoline to pyridine and that of 2,4-lutidine to gamma-picoline were also promoted greatly upon gamma-ray irradiation at room temperature in air in the presence of both methanol and nickel nitrate.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Treatment of (R)-[{alpha-(dimethylamino)ethyl}-eta6-benzene]Cr(CO)3 with esters of chloroformic acid leads to stereoselective substitution of the dimethylamino group for a chloro substituent. The reaction can be extended to systems in which the chromium arene complex, after metalation, is diastereoselectively substituted in the ortho position with carbon and silicon electrophiles to generate planar chirality. The chloro group in turn can be replaced stereoselectively for various phosphorus, nitrogen, and oxygen nucleophiles. Both substitution reactions in the benzylic position proceed via retention of configuration. The addition of cyanide is not stereospecific. The phosphine derivatives are efficient catalysts for the enantioselective hydrovinylation of styrene to 3-phenyl-1-butene. X-ray crystal structures establish the absolute configuration of (R)-[(alpha-chloroethyl)eta6-benzene]Cr(CO)3, (R)-[{alpha-(diphenylphosphanyl)ethyl}-alpha6-benzene]Cr(CO) 3, and (pS,S)-[l-(alpha-cyanoethyl)-2-methyl-eta6-benzene]Cr(CO) 3.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis