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Influence of steric effect on the structural aspects of N,N?,N?-triarylguanidine derived six-membered [C,N] palladacycles

Guanidine derived six-membered [C,N] palladacycles of the types [(C,N)Pd(mu-OC(O)R)]2 (1a-d), [(C,N)Pd(mu-Br)]2 (2a,b), cis-[(C,N)PdBr(L)] (3a-d, 4, and 5), and ring contracted guanidine derived five-membered [C,N] palladacycle, [(C,N)PdBr(CNXy)] (6) were prepared in high yield following the established methods with a view aimed at understanding the influence of the substituents on the aryl rings of the guanidine upon the solid state structure and solution behaviour of palladacycles. Palladacycles were characterised by microanalytical, IR, NMR and mass spectral data. The molecular structures of 1a, 1c, 2a, 2b, 3a, 3c, 3d, and 4-6 were determined by single crystal X-ray diffraction data. Palladacycles 1a and 1c were shown to exist as a dimer in transoid in-in conformation in the solid state but as a mixture of a dimer in major proportion and a monomer (kappa2-O, O?-OAc) in solution as deduced from 1H NMR data. Palladacycles 2a and 2b were shown to exist as a dimer in transoid conformation in the solid state but the former was shown to exist as a mixture of a dimer and presumably a trimer in solution as revealed by a variable temperature 1H NMR data in conjunction with ESI-MS data. The cis configuration around the palladium atom in 3a, 3c, and 3d was ascribed to steric influence of the aryl moiety of NAr unit and that in 4-6 was ascribed to antisymbiosis. The solution behaviour of 3d was studied by a variable concentration (VC) 1H NMR data.

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

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Utilizing proton transfer to produce molecular salts in bromanilic acid substituted-pyridine molecular complexes-predictable synthons?

Controlled introduction of proton transfer into the design of a series of molecular complexes is described, delivering the systematic production of ionic molecular complexes (molecular salts). The controlled production of molecular salts has relevance as a potential strategy in the design of pharmaceutical materials. In nine molecular complexes consisting of bromanilic acid with the N-heterocyclic compounds 2-, 3-and 4-picoline [bis(2/3/4-methylpyridinium) 2,5-dibromo-3,6-dioxocyclohexa-1,4-diene-1,4-diolate, 2C6H 8N+¡¤C6Br2O4 2-], 2,3-, 2,4-, 2,5-and 3,5-lutidine [2,3/2,4/2,5/3,5- dimethylpyridinium 2,5-dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1-olate, C7H10N+¡¤C6HBr 2O4 -], and 3-bromo-4-methylpyridine [3-bromo-4-methylpyridinium 2,5-dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1- olate, C6H7BrN+¡¤C6HBr 2O4 -] and 2-bromo-3-methylpyridine [2-bromo-3-methylpyridine-2,5-dibromo-3,6-dihydroxycyclohexa-2,5-diene-1, 4-dione (1/1), C6H6BrN¡¤C6H 2Br2O4], proton transfer occurs readily between the bromanilic acid molecule and the N heteroatom of the pyridine ring, in all cases producing a charge-assisted bifurcated N-H…O hydrogen bond. This reinforces the value of this motif as a design tool in the crystal engineering of such complexes. The protonation state (and stoichiometry) significantly affect the supramolecular synthons obtained, but 1:2 stoichiometries reliably give rise to PBP synthons and 1:1 stoichiometries to PBBP synthons (where P indicates a methylpyridine co-molecule and B a bromanilic acid molecule). The influence of halogen interactions on the wider crystal packing is also discussed, with C-H…Br and Br…O interactions the most prevalent; only one Br…Br interaction is found.

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

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Preparation of chiral multifunctional thiourea-phosphanes and synthesis of chiral allylic phosphites and phosphane oxides through asymmetric allylic substitution reactions of morita-baylis-hillman carbonates

We developed a synthetic method to prepare chiral multifunctional thiourea-phosphane catalysts for the asymmetric allylic substitution reaction of Morita-Baylis-Hillman carbonates with diphenyl phosphite or diphenylphosphane oxide to give allylic phosphites and allylic phosphane oxides in high yields with excellent enantioselectivity.

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

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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Application In Synthesis of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 126456-43-7, name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol. In an article£¬Which mentioned a new discovery about 126456-43-7

Diversification of ortho-Fused Cycloocta-2,5-dien-1-one Cores and Eight- to Six-Ring Conversion by sigma Bond C?C Cleavage

Sequential treatment of 2-C6H4Br(CHO) with LiC?CR1(R1=SiMe3, tBu), nBuLi, CuBr?SMe2and HC?CCHClR2[R2=Ph, 4-CF3Ph, 3-CNPh, 4-(MeO2C)Ph] at ?50 C leads to formation of an intermediate carbanion (Z)-1,2-C6H4{CA(=O)C?CBR1}{CH=CH(CH?)R2} (4). Low temperatures (?50 C) favour attack at CBleading to kinetic formation of 6,8-bicycles containing non-classical C-carbanion enolates (5). Higher temperatures (?10 C to ambient) and electron-deficient R2favour retro sigma-bond C?C cleavage regenerating 4, which subsequently closes on CAproviding 6,6-bicyclic alkoxides (6). Computational modelling (CBS-QB3) indicated that both pathways are viable and of similar energies. Reaction of 6 with H+gave 1,2-dihydronaphthalen-1-ols, or under dehydrating conditions, 2-aryl-1-alkynylnaphthlenes. Enolates 5 react in situ with: H2O, D2O, I2, allylbromide, S2Me2, CO2and lead to the expected C-E derivatives (E=H, D, I, allyl, SMe, CO2H) in 49?64 % yield directly from intermediate 5. The parents (E=H; R1=SiMe3, tBu; R2=Ph) are versatile starting materials for NaBH4and Grignard C=O additions, desilylation (when R1=SiMe) and oxime formation. The latter allows formation of 6,9-bicyclics via Beckmann rearrangement. The 6,8-ring iodides are suitable Suzuki precursors for Pd-catalysed C?C coupling (81?87 %), whereas the carboxylic acids readily form amides under T3P conditions (71?95 %).

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

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Reference of 108-47-4, Chemistry is the experimental science by definition. We want to make observations to prove hypothesis. For this purpose, we perform experiments in the lab. 108-47-4, Name is 2,4-Dimethylpyridine,introducing its new discovery.

Solvent Effect on CuCl2-Pyridine Derivative Complexes: UV-VIS ans E.S.R. Study of the CuCl2-2,4-Dimethylpyridine-Solvent Systems

The electronic (400 – 800 nm; 298.2 K) and E.S.R. spectra (298 K; 77K) have been measured for CuCl2-2,4-dimethylpyridine(2,4-Me2py)-solvent systems (solvents: aliphatic and aromatic hydrocarbons, carbon tetrachloride, chloroform, 1,1,2,2-tetrachloroethane).In all the media CuCl2 forms electrically neutral strongly distorted six-coordinated complexes, the extent of tetragonality being greater than for analogous complexes with non-alpha-substituted pyridines.In contrast to aliphatic and aromatic hydrocarbons protic solvents and, unexpectedly, aprotic carbon tetrachloride solvate the CuCl2-Me2py complex comparatively strongly, most probably through interactions with the chlorine ligand.The results for 2,4-Me2py were compared with those for pyridine, 4-ethylpyridine and isoquinoline and discussed in terms of steric effects on solvation.In particular, alpha-substitution seems to hinder the solvation of the complex by the amine. – Keywords: Solvent effect; Copper(II) chloride complexes; Pyridine derivative complexes

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

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Liquid Chromatographic Study of Solute Hydrogen Bond Basicity

The purpose of the present work was to investigate a liquid chromatographic method for the measurement of relative hydrogen bond basicities of dilute species. This type of determination cannot be done with conventional reversed-phase liquid chromatography due to the silanophilic interactions of basic solutes with the silica packing material. The studies were done on a polymeric stationary phase with pendant phenol groups that act as powerful hydrogen bond donors. Solute retention was evaluated in terms of two hydrogen bond basicity scales, beta2H and beta2C, and a steric hindrance parameter, Es. beta2H and beta2C are basicity scales based on the free energy of forming 1:1 hydrogen bond complexes and the retention on a strong hydrogen bond donor gas chromatographic phase, respectively. The Es parameter characterizes the steric effect experienced by the solute acceptor site. It is shown that retention correlates very strongly with beta2H and less strongly with beta2C. The log k? values need only two descriptive parameters, i.e., beta2H and Es, to give a good fit. As a whole, retention on the phenolic polymeric phase provides an efficient method for the measurement of relative hydrogen bond basicities.

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

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Micro-structured reactors as a tool for chiral modifier screening in gas-liquid-solid asymmetric hydrogenations

A continuous micro-structured reactor equipped with a perforated (5 mum) membrane is used for the investigation of the gas-liquid-solid asymmetric hydrogenation of ethylpyruvate on a Pt/gamma-Al2O3 catalyst modified with chiral inductors under high hydrogen pressure (45 bar). Up to eight chiral inductors have been evaluated, the best enantioselectivity (63%) being obtained with cinchonidine. The very low reaction volume (100 mul) offers short operating time. Solvent effect, deactivation studies and the effect of modifier leaching are also reported.

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

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Carbon-Hydrogen Bond Dissociation Energies in Alkylbenzenes. Proton Affinities of the Radicals and the Absolute Proton Affinity Scale

Rate constants (k) were measured for proton-transfer reactions from alkylbenzene ions RH+ to a series of reference bases B, i.e., RH+ + B -> BH+ + R*.For exothermic reactions (DeltaH BH+ + C6H5CH2* is fast (reaction efficiency = k/kcol >/= 0.5) when B = MeO-t-Bu or stronger bases, but k/kcol is significantly smaller when B is n-Pr2O or weaker bases.From the falloff curve of reaction efficiency vs.PA(B), we find PA(n-Pr2O) = PA(C6H5CH2*) + 0.8 kcal mol-1 = 200.0 kcal mol-1.Since PA(C6H5CH2*) is obtained from known thermochemical data, this relation defines the absolute PA of n-Pr2O.Through a ladder of known PA, we then obtain PA(i-C4H8) = 186.8 kcal mol-1; we also obtain the absolute PAs of other oxygen bases.Falloff curves of reaction efficiencies of 3-FC6H4CH3+, C6H5C2H5+, C6H5-n-C3H7+, and C6H5-i-C3H7+ with these reference bases give then the following PAs of R* and R-H bond dissociation energies (Do) (all in kcal mol-1) as R*, PA(R*), Do(R-H): 3-FC6H4CH2*, 197.2, 89.4; , 197.9, 86.2; , 199.1, 86.1; , 199.6, 86.1.In similar manner, rate constants for H+ transfer from C6H5NH2+ to reference pyridines and amines yield PA(C6H5NH*) = 221.5 and Do(C6H5NH-H) = 85.1 kcal mol-1 (1 kcal mol-1 = 4.18 kJ mol-1).

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

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Synthetic Route of 108-47-4, A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 108-47-4, Name is 2,4-Dimethylpyridine, molecular formula is C7H9N. In a Article£¬once mentioned of 108-47-4

Heteroassociation of Selected Diols with some Tertiary Amines

Diols exhibiting the structure (HO)CH2-(CH2) n-CH2(OH) with n = 1 up to n = 4, (HO)CH 2-CH(OH)-CH3 and cyclohexan-1,2-diols as well as cyclohexan-1,4-diol, which may establish different intramolecular interactions, are used as model substances to describe the external hydrogen bonding behaviour of multivalent hydrogen bond donors in the presence of hydrogen bond acceptor molecules. In this study, hydrogen bonds formed by the diols with tertiary aromatic amines have been investigated. In solution, different associate formation between the diols and the acceptor molecules as sketched in Fig. 1 may occur. Besides 1:1 associates formed by the interaction of one diol molecule with one amine molecule, 1:2 associates may be observed where each OH function interacts with one amine molecule. The equilibrium constants of the associates of those interactions have been studied by FTIR spectroscopy. The results allow a classification of the used diols in three different groups based on the position of the OH groups in the donor molecule. For diols with proton donating OH where no intramolecular hydrogen bond can be formed, the intermolecular hydrogen bonds for a 1:1 system may be described by thermodynamic parameters which are nearly twice the value of the corresponding equilibrium constants of monovalent alcohol systems due to the statistical weight of the OH groups. Secondly, when intramolecular hydrogen bond exists in the diols, the equilibrium constants in the interaction with the amine raise up by a factor of ca. 2-3 due to the cooperativity effect. Thirdly, if the OH groups are arranged in 1,2 positions, both OH groups may be described as independent of each other in their intermolecular interaction with the amine.

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

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Substituted imidazoles as glucagon receptor antagonists

A modestly active, nonselective triarylimidazole lead was optimized for binding affinity with the human glucagon receptor. This led to the identification of a 2- and/or 4-alkyl or alkyloxy substituent on the imidazole C4-aryl group as a structural determinant for significant enhancement in binding with the glucagon receptor (e.g., 41, IC50 = 0.053 muM) and selectivity (> 1000 ¡Á) over p38 MAP kinase in this class of compounds.

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