Naryl-substituted anthranilamides with intramolecular hydrogen bonds

Hydrogen bonding interaction as one type of non-covalent force has proven itself to be highly efficient for constructing structurally unique artificial secondary structures. Here, the structure of N_aryl-substituted anthranilamide in solution is demonstrated by various NMR technique, the intramolecular hydrogen bonds between amide attached to arylamine of the same ring is proposed, which is supported by its crystal structure in the solid phase. The substituent on the nitrogen atom of arylamine plays an important role in forming the presence of intramolecular hydrogen bonds. The chemical shift of the N_aryl-H downfield changes obviously, due to the formation of intramolecular hydrogen bonds and the deshielding effect of oxygen, and the neighboring C–H is activated and shows downfield protonic signal too. The presence of intramolecular hydrogen bonds probably provides the explanation for the transformation from N_aryl-substituted anthranilamide to imine, which could be converted into 2-aryl quinazolinone finally.     

Pd‐Catalyzed Reaction of Allyl Carbonate with Polyols: The Role of CO2 in Transesterification versus Etherification of Glycerol

An intermolecular Pd/PPh₃‐catalyzed transesterification of diallyl carbonate with glycerol to generate glycerol carbonate has been developed. Analysis of the reaction kinetics in THF indicates a first‐order dependence on Pd and diallyl carbonate, that the Pd bears two phosphines during the turnover limiting event, and that increasing the glycerol concentration inhibits reaction, possibly via change in the polarity of the medium. ¹³C isotopic labeling studies demonstrate that the Pd‐catalyzed transesterification requires at least one allyl carbonate moiety and that there is rapid equilibrium of the allyl carbonate with CO₂ in solution, even when present only at low concentrations. A mechanism that is consistent with these results involves oxidative addition of the allyl carbonate to Pd followed by reversible decarboxylation, with the intermediate η¹‐ and η³‐allyl Pd alkoxides mediating direct and indirect transesterification reactions with the glycerol. Using this model, successful simulations of the kinetics of reactions conducted under atmospheres of N₂ or CO₂ could be achieved, including switching in selectivity between etherification and transesterification in the early stages of reaction. Reactions with the higher polyols threitol and erythritol are also efficient, generating the terminal (1,2) monocarbonates with high selectivity.     

Theoretical study of the excited singlet and triplet states of alloxan

The possibility of excited‐state protomeric shifts in the biologically important molecule, alloxan, is investigated. We have focused on the S₁ and T₁ excited states of alloxan and its hydroxy tautomers. Modifications brought in by excitation on the relative stabilities, activation barriers, and optimized geometries, computed at the MNDO, AM1, and PM3 levels of approximation, have been discussed for both excited electronic states. The absorption and fluorescence spectra for the three tautomers are also discussed. Results show significant changes in the geometries on excitation, although the changes are similar for the singlet and triplet excited states. Though the relative stability orders do not change, the 2‐hydroxy tautomer is stabilized, while the 4‐hydroxy tautomer gets destabilized on excitation. The excited states are (n,π*) states, involving the promotion of a nonbonding oxygen lone pair from the CO? CO? CO moiety, which explains why the oxygens of this group become less basic and the 4‐hydroxy tautomer gets destabilized on excitation. However, the activation barriers do not reduce significantly on excitation, and this precludes the possibility of ground‐ or excited‐state proton transfer in the gas phase. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Light-induced cis/trans isomerization of cis-[Pd(L-S,O)2] and cis-[Pt(L-S,O)2] complexes of chelating N,N-dialkyl-N′-acylthioureas: key to the formation and isolation of trans isomers

Irradiation cis-[M(Lⁿ-S,O)₂] complexes (M = Pt^II, Pd^II) derived from N,N-dialkyl-N′-benzoylthioureas (HLⁿ) with various sources of intense visible polychromatic or monochromatic light with λ < 500 nm leads to light-induced cis?→?trans isomerization in organic solvents. In all cases, white light derived from several sources or monochromatic blue-violet laser 405 nm light, efficiently results in substantial amounts of the trans isomer appearing in solution, as shown by ¹H NMR and/or reversed-phase HPLC separation in dilute solutions at room temperature. The extent and relative rates of cis/trans isomerization induced by in situ laser light (λ = 405 nm) of cis-[Pd(L²-S,O)₂] was directly monitored by ¹H NMR and ¹⁹⁵Pt NMR spectroscopy of selected cis-[Pt(L-S,O)₂] compounds in chloroform-d; both with and without light irradiation allows the δ(¹⁹⁵Pt) chemical shifts cis/trans isomer pairs to be recorded. The cis/trans isomers appear to be in a photo-thermal equilibrium between the thermodynamically favored cis isomer and its trans counterpart. In the dark, the trans isomer reverts back to the cis complex in what is probably a thermal process. The light-induced cis/trans process is the key to preparing and isolating the rare trans complexes which cannot be prepared by conventional synthesis as confirmed by the first example of trans-[Pd(L-S,O)₂] characterized by single-crystal X-ray diffraction, deliberately prepared after photo-induced isomerization in acetonitrile solution.     

Direct Access to Aryl Bis(trifluoromethyl)carbinols from Aryl Bromides or Fluorosulfates: Palladium‐Catalyzed Carbonylation

A palladium‐catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α‐bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late‐stage carbon‐isotope labeling.     

Enhanced Sensitivity to Local Dynamics in Peptides by Use of Temperature-Jump IR Spectroscopy and Isotope Labeling

Site-specific isotopic labeling of molecules is a widely used approach in IR spectroscopy to resolve local contributions to vibrational modes. The induced frequency shift of the corresponding IR band depends on the substituted masses, as well as on hydrogen bonding and vibrational coupling. The impact of these different factors was analyzed with a designed three-stranded β-sheet peptide and by use of selected ¹³C isotope substitutions at multiple positions in the peptide backbone. Single-strand labels give rise to isotopically shifted bands at different frequencies, depending on the specific sites; this demonstrates sensitivity to the local environment. Cross-strand double- and triple-labeled peptides exhibited two resolved bands that could be uniquely assigned to specific residues, the equilibrium IR spectra of which indicated only weak local-mode coupling. Temperature-jump IR laser spectroscopy was applied to monitor structural dynamics and revealed an impressive enhancement of the isotope sensitivity to both local positions and coupling between them, relative to that of equilibrium FTIR spectroscopy. Site-specific relaxation rates were altered upon the introduction of additional cross-strand isotopes. Likewise, the rates for the global β-sheet dynamics were affected in a manner dependent on the distinct relaxation behavior of the labeled oscillator. This study reveals that isotope labels provide not only local structural probes, but rather sense the dynamic complexity of the molecular environment.     

2-甲基-6-乙酰基萘结构的表征

2-甲基-6-乙酰基萘是一种有发展前景的化工产品。本实验在合成和精制的基础上,采用气相色谱、质谱、^1H、^13C及二维核磁共振技术表征了2-甲基-6-乙酰基萘的结构,首次给出了该化合物的化学位移数据。     

Local protein backbone folds determined by calculated NMR chemical shifts

NMR chemical shifts (CSs: δN(NH), δC(α), δC(β), δC', δH(NH), and δH(α)) were computed for the amino acid backbone conformers (α(L), β(L), γ(L), δ(L), ε(L), α(D), γ(D), δ(D), and ε(D) [Perczel et al., J Am Chem Soc 1991, 113, 6256]) modeled by oligoalanine structures. Topological differences of the extended fold were investigated on single β-strands, hairpins with type I and II β-turns, as well as double- and triple-stranded β-sheet models. The so-called "capping effect" was analyzed: residues at the termini of a homoconformer sequence unit usually have different CSs than the central residues of an adequately long homoconformer model. In heteroconformer sequences capping effect ruins the direct applicability of several chemical shift types (δH(NH), δC', and δN(NH)) for backbone structure determination of the parent residue. Experimental δH(α), δC(α), and δC(β) values retrieved from protein database are in good agreement with the relevant computed data in the case of the common backbone conformers (α(L), β(L), γ(L), and ε(L)), even though neighboring residue effects were not accounted for. Experimental and computed ΔδH(α)-ΔδC(α), ΔδH(α)-ΔδC(β), and ΔδC(α)-ΔδC(β) maps give qualitatively the same picture, that is, the positions of the backbone conformers relative to each other are very similar. This indicates that the H(α), C(α), and C(β) chemical shifts of alanine depend considerably on the backbone fold of the parent residue also in proteins. We provide tabulated CSs of the chiral amino acids that may predict the various structures of the residues.     

“Through-Space” Relativistic Effects on NMR Chemical Shifts of Pyridinium Halide Ionic Liquids

We have investigated, using two-component relativistic density functional theory (DFT) at ZORA-SO-BP86 and ZORA-SO-PBE0 level, the occurrence of relativistic effects on the ¹H, ¹³C, and ¹⁵N NMR chemical shifts of 1-methylpyridinium halides [MP][X] and 1-butyl-3-methylpyridinium trihalides [BMP][X₃] ionic liquids (ILs) (X=Cl, Br, I) as a result of a non-covalent interaction with the heavy anions. Our results indicate a sizeable deshielding effect in ion pairs when the anion is I⁻ and I₃⁻. A smaller, though nonzero, effect is observed also with bromine while chlorine based anions do not produce an appreciable relativistic shift. The chemical shift of the carbon atoms of the aromatic ring shows an inverse halogen dependence that has been rationalized based on the little C-2s orbital contribution to the σ-type interaction between the cation and anion. This is the first detailed account and systematic theoretical investigation of a relativistic heavy atom effect on the NMR chemical shifts of light atoms in the absence of covalent bonds. Our work paves the way and suggests the direction for an experimental investigation of such elusive signatures of ion pairing in ILs.     

Effects of dynamical couplings in hydrogen bond systems in the polarized IR spectra of 3-hydroxybenzaldehyde and 4-hydroxybenzaldehyde crystals

This paper presents the investigation results of the polarized IR spectra of 3-hydroxybenzaldehyde and 4-hydroxybenzaldehyde crystals measured at 293 and 77 K. Analysis of the results concerned the linear dichroic, H/D isotopic and temperature effects observed in the spectra of the hydrogen and deuterium bond at the frequency ranges of the ν_O–H and the ν_O–D bands, respectively. The main spectral properties of the crystals were interpreted in terms of the “strong-coupling” theory on the basis of the hydrogen bond dimer model. The spectra revealed that the strongest vibrational exciton coupling involved the closely-spaced hydrogen bonds, each belonging to a different chain of associated molecules. The reason for two different crystalline systems, are characterized by almost identical ν_O–H and ν_O–D band shapes, is explained. It was proved that a random distribution of the protons and deuterons took place in the lattices of the isotopically diluted crystals.