Discovery of C7H9N

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Structural and 1H, 13C, 15N NMR spectroscopic studies of Pd(II) chloride organometallics with 2-phenylpyridine and ammonia, pyridine or its methyl derivatives

Pd(II) chloride organometallics with 2-phenylpyridine and pyridines of general formula [Pd(2ppy?)LCl] (2ppy? = C(2?)-deprotonated form of 2-phenylpyridine (2ppy), acting as N(1),C(2?)-chelating ligand; L = NH3, pyridine, 2-, 3-, 4-methylpyridine, 2,3-, 2,4-, 2,6-, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine) were studied by 1H, 13C and 15N NMR. 1H, 13C and 15N NMR coordination shifts (i.e. differences of chemical shifts for the same atom in the complex and ligand molecules) were discussed in relation to the molecular structures. Single crystal X-ray structure of trans(N,N)-[Pd(2ppy?)(2,4,6col)Cl] was solved. The analysis of 15N NMR coordination shifts for the whole series of the studied organometallics exhibited that all of them had an analogous trans(N,N) geometry.

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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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Process for the separation of a mixture of enantiomers

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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Cyclic Tetrapeptides Bearing a Sulfhydryl Group Potently Inhibit Histone Deacetylases

(Equation presented) New inhibitors of histone deacetylase (HDAC) containing a sulfhydryl group were designed on the basis of the corresponding hydroxamic acid (CHAP31) and FK228. Their disulfide dimers and hybrids exhibited potent HDAC inhibitory activity in vivo with potential as anticancer prodrugs.

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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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Intramolecular Photocyclization of N-<(2-Haloaryl)methyl>pyridinium and N-(Arylmethyl)-2-halopyridinium Salts

Various N-<(2-haloaryl)methyl>pyridinium, N-(arylmethyl)-2-halopyridinium and N-(2-halobenzyl)isoquinolinium salts have been synthesized and their intramolecular photocyclization reactions studied.Upon irradiation the aqueous solution of N-<(2-haloaryl)methyl>pyridinium and N-arylmethyl-2-halopyridinium salts 1, 2 were cyclized to give isoindolium salts.In contrast to the pyridinium salts 1, 2, the aqueous solution of N-(2-halobenzyl)isoquinolinium salts 3 appear not to undergo photocyclization.N-Benzyl-2-chloropyridinium salts 1c is more reactive than N-(2-chlorobenzyl)pyridinium salt 1a in the photocyclization.N-(2-Chlorobenzyl)-2-chloropyridinium salt 1d is three times more reactive than 1c.A mechanism of ?-complex formation of the halogen moiety of the pyridinium ring with the phenyl ring is suggested for the reactive pyridinium salt.The triplet energy of the isoquinolinium salts 3 is too low to photocyclize.

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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

Extracurricular laboratory:new discovery of 2,4-Dimethylpyridine

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Proton transfer rate-equilibria in apolar aprotic solvents: a historical perspective

Low dielectric constant apolar aprotic solvents, although employed on a limited scale for studying proton transfer reactions as compared with commonly used polar protic or dipolar aprotic ones, offer some particular advantages, namely, specific solute?solvent interactions are virtually eliminated and proton transfer occurs directly in an apolar aprotic solvent. An intriguing feature of these reactions is their general acid-catalyzed/base-catalyzed kinetics with a time scale over microseconds to minutes. In fact, the true or intrinsic relative strengths of acids/bases when measured in such solvents come to the fore much more clearly than those obtained in other classes of solvents. Recently, a review documenting the post-1980 developments relating to proton transfer reactions in apolar aprotic solvents has been published. The present article is a commentary of the pre-1980 developments in this area since the 1920s Br°nsted?Lowry’s ?proton cult? of acid?base theory. Copyright

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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

Brief introduction of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Diversity-Oriented Synthesis of Diol-Based Peptidomimetics as Potential HIV Protease Inhibitors and Antitumor Agents

Peptidomimetic HIV protease inhibitors are an important class of drugs used in the treatment of AIDS. The synthesis of a new type of diol-based peptidomimetics is described. Our route is flexible, uses d-glucal as an inexpensive starting material, and makes minimal use of protection/deprotection cycles. Binding affinities from molecular docking simulations suggest that these compounds are potential inhibitors of HIV protease. Moreover, the antiproliferative activities of compounds 33 a, 35 a, and 35 b on HT-29, M21, and MCF7 cancer cell lines are in the low micromolar range. The results provide a platform that could facilitate the development of medically relevant asymmetrical diol-based peptidomimetics.

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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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Direct one-pot introduction of 2-methylpyridines to Baylis-Hillman adducts via base-mediated 3-aza-Cope rearrangement

An efficient and regioselective introduction method of 2-methylpyridines to the secondary position of Baylis-Hillman adducts has been developed. A base treatment of 2-methylpyridinium salt of Baylis-Hillman bromide generated N-allylenamine intermediate which underwent a facile 3-aza-Cope rearrangement under mild conditions to produce the product.

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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

Final Thoughts on Chemistry for (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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An efficient approach to homochiral indane nucleosides

A series of new chiral 6-substituted purinyl and 8-aza-purinyl carbonucleosides based on indanol were synthesized from the commercially available (1R,2S)-1-amino-2-indanol and (1S,2R)-1-amino-2-indanol based on a well-known methodology.

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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 detection of chemically induced chromosomal malsegregation in Saccharomyces cerevisiae D61.M: A literature survey (1984-1990)

Our objective is to summarize the published data obtained with a recently developed tester strain suitable for the detection of chromosomal malsegregation in yeast. Results from 25 papers were reviewed in which numerical data for 111 chemicals tested in Saccharomyces cerevisiae D61.M are reported (a total of 316 independent tests; 279 acceptable, 37 not meeting our criteria). Of the 111 compounds analyzed 43 compounds are positive for chromosomal malsegregation, 56 compounds are negative and 12 compounds do not meet our criteria for acceptance (inconclusive). Of the 43 compounds judged positive 5 (acetone, acetonitrile, benzonitrile, ethylacetate and propionitrile) were only positive using a cold interruption protocol. Recommendations are made for standardization of methods and protocols for screening purposes. Finally, a comparison with in vitro tubulin assembly data using mammalian tubulin is presented.

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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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Carbocationic polymerization: Mechanisms and kinetics of propagation reactions

Propagation rate constants kp in carbocationic polymerizations can be obtained through two general methods. The first one, used for decades, calculated kp from the polymerization rates and from the ionic species concentrations (ISC) measured or estimated in various ways. The second one, used during the last 10 years, is based on the diffusion-clock (DC) assumption, in which competitive reactions between propagation with the monomer and termination with another nucleophile N permit to calculate kp if termination is a diffusion-controlled reaction (with e.g. kN=k diff=3×109 L mol-1 s-1 in CH2Cl2 solution). A problem arises since the k p obtained by this last method with, e.g. styrene and isobutylene are 104 to 105 times larger than those obtained earlier in solution by the ISC method, and the aim of this article is to try to explain this discrepancy. The different methods of measurement of the second-order rate constants of propagation kp+ or kp±, respectively, on unpaired ions and ion-pairs are examined in Sections 2 and 4 and compared in Section 3 with the rate constants of model reactions. The validity of the kp+ and kp± determinations by the two methods are compared (Section 6), but results are unfortunately obtained only by the DC method for styrene, p-chlorostyrene and p-methylstyrene with kp±?109Lmol-1s-1, and by the ISC method for most other monomers with kp± between 104 and 105 L mol-1 s-1. It is shown that the large difference between these two sets of values as well as that between the parameters of ionization Ki, ki and k-i of the terminal halides in living polymerizations (Section 5) cannot be explained quantitatively by the large electrophilicity of the carbocation of these poly(styrene)s. Diffusion-controlled propagation for styrene is also in contradiction with reactivity ratios and rates of copolymerization with various monomers. The recent measurements of kp± in living polymerizations of several monomers have confirmed the validity of the kp± obtained earlier from non-living systems and based on the ionic species concentration. It is concluded that kp± for styrene should be of a similar order of magnitude. In order to have a comprehensive view interpreting all experimental results, the hypothesis has been made of competitive termination (and possibly propagation) occurring as two-steps reactions, the first step being a complexation of the growing carbocation with the nucleophile, giving a resonance stabilized complex, and the second step a unimolecular rearrangement of the complex.

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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