Evolution of amide stacking in larger γ-peptides: triamide H-bonded cycles

The single-conformation spectroscopy of two model γ-peptides has been studied under jet-cooled conditions in the gas phase. The methyl-capped triamides, Ac-γ(2)-hPhe-γ(2)-hAla-NHMe and Ac-γ(2)-hAla-γ(2)-hPhe-NHMe, were probed by resonant two-photon ionization (R2PI) and resonant ion-dip infrared (RIDIR) spectroscopies. Four conformers of Ac-γ(2)-hPhe-γ(2)-hAla-NHMe and three of Ac-γ(2)-hAla-γ(2)-hPhe-NHMe were observed and spectroscopically interrogated. On the basis of comparison with the predictions of density functional theory calculations employing a dispersion-corrected functional (ωB97X-D/6-311++G(d,p)), all seven conformers have been assigned to particular conformational families. The preference for formation of nine-membered rings (C9) observed in a previous study [James, W. H., III et al., J. Am. Chem. Soc. 2009, 131, 14243] of the smaller analog, Ac-γ(2)-hPhe-NHMe, carries over to these triamides, with four of the seven conformers forming C9/C9 sequential double-ring structures, and one conformer a C9/C14 bifurcated double ring. The remaining two conformers form C7/C7/C14 H-bonded cycles involving all three amide NH groups, unprecedented in other peptides and peptidomimetics. The amide groups in these structures form a H-bonded triangle with the two trimethylene bridges forming loops above and below the molecule's midsection. The structure is a natural extension of amide stacking, with the two terminal amides blocked from forming the amide tristack by formation of the C14 H-bond. Pair interaction energy decomposition analysis based on the fragment molecular orbital method (FMO-PIEDA) is used to determine the nonbonded contributions to the stabilization of these conformers. Natural bond orbital (NBO) analysis identifies amide stacking with a pair of n → π* interactions between the nitrogen lone pairs and π* orbitals on the carbonyl of the opposing amide groups.     

Radical cations of disubstituted cyclopropanes: stereoelectronic effects on hyperfine coupling

The positive hyperfine coupling constants of the geminal ¹H nuclei in cis‐1,2‐dimethyl‐ and cis‐1,2‐diphenylcyclopropane radical cations show a significant stereoelectronic effect: the ¹H nuclei trans (anti) to the substituents are coupled much more strongly than the corresponding nuclei cis (syn) to them. Theoretical calculations on these radical cations and on bismethano[2,2]paracylophane as well as new ¹H‐CIDNP experiments at 200 Mz elucidate the general features of these systems. Copyright © 2014 John Wiley & Sons, Ltd.     

Total Synthesis of (18S)‐ and (18R)‐Homolargazole by Rhodium‐Catalyzed Hydrocarboxylation

Homolargazole derivatives, in which the macrocycle of natural largazole is extended by one methylene group, were prepared by the recently developed rhodium‐catalyzed hydrocarboxylation reaction onto allenes. This strategy gives access to both the (18S)‐ and (18R)‐stereoisomers in high stereoselectivity under ligand control.     

Evolution of a heavy rigid body rotation under the action of unsteady restoring and perturbation torques

The paper develops an approximate solution to the system of Euler’s equations with additional perturbation term for dynamically symmetric rotating rigid body. The perturbed motions of a rigid body, close to Lagrange’s case, under the action of restoring and perturbation torques that are slowly varying in time are investigated. We describe an averaging procedure for slow variables of a rigid body perturbed motion, similar to Lagrange top. Conditions for the possibility of averaging the equations of motion with respect to the nutation phase angle are presented. The averaging technique reduces the system order from 6 to 3 and does not contain fast oscillations. An example of motion of the body using linearly dissipative torques is worked out to demonstrate the use of general equations. The numerical integration of the averaged system of equations is conducted of the body motion. The graphical presentations of the solutions are represented and discussed. A new class of rotations of a dynamically symmetric rigid body about a fixed point with account for a nonstationary perturbation torque, as well as for a restoring torque that slowly varies with time, is studied. The main objective of this paper is to extend the previous results for problem of the dynamic motion of a symmetric rigid body subjected to perturbation and restoring torques. The proposed averaging method is implemented to receive the averaging system of equations of motion. The graphical representations of the solutions are presented and discussed. The attained results are a generalization of our former works where µ and M_i are independent of the slow time τ and M_i depend on the slow time only.

     

Synthesis, structural and hydrogenation properties of Mg-rich MgH2-TiH2 nanocomposites prepared by reactive ball milling under hydrogen gas

MgH(2)-TiH(2) nanocomposites have been obtained by reactive ball milling of elemental powders under 8 MPa of hydrogen pressure. The composites consist of a mixture of β-rutile MgH(2), γ-orthorhombic high pressure MgH(2) and ε-tetragonal TiH(2) phases with nanosized crystallites ranging from 4 to 12 nm. In situ hydrogen absorption curves on milling reveal that nanocomposite formation occurs in less than 50 min through the consecutive synthesis of the TiH(2) and MgH(2) phases. The abrasive and catalytic properties of TiH(2) speed up the formation of the MgH(2) phase. Thermodynamic, kinetic and cycling hydrogenation properties have been determined for the 0.7MgH(2)-0.3TiH(2) composite and compared to nanometric MgH(2). Only the MgH(2) phase desorbs hydrogen reversibly at moderate temperature (523 to 598 K) and pressure (10(-3) to 1 MPa). The presence of TiH(2) does not modify the thermodynamic properties of the Mg/MgH(2) system. However, the MgH(2)-TiH(2) nanocomposite exhibits outstanding kinetic properties and cycling stability. At 573 K, H-sorption takes place in less than 100 s. This is 20 times faster than for a pure nanometric MgH(2) powder. We demonstrate that the TiH(2) phase inhibits grain coarsening of Mg, which allows extended nucleation of the MgH(2) phase in Mg nanoparticles before a continuous and blocking MgH(2) hydride layer is formed. The low crystallinity of the TiH(2) phase and its hydrogenation properties are also compatible with a gateway mechanism for hydrogen transfer from the gas phase to Mg. Mg-rich MgH(2)-TiH(2) nanocomposites are an excellent media for hydrogen storage at moderate temperatures.     

Interaction of 2'-deoxyadenosine with cis-2-butene-1,4-dial: computational approach to analysis of multistep chemical reactions

The computational analysis of multistep chemical interactions between 2'-deoxyadenosine and cis-2-butene-1,4-dial has been performed. The applied protocol includes generation of a multistep Gibbs free-energy reaction profile (PCM/M05-2X/6-311+G(d) level) for the transformations of the reagents to products, followed by evaluation of the rate constants, construction of the corresponding kinetic equations, and solving them. Such a procedure allows one to significantly extend the number of experimentally determined steps by addition of the ones computationally predicted. The primary products of the reaction are found to be four diastereomeric adducts characterized by virtually the same stability. The acid-catalyzed dehydration of these adducts leads to a more stable secondary product. Computational verification of UV and NMR spectra has also been performed. It has been revealed that simulated UV and NMR spectra of primary and secondary 2'-deoxyadenosine adducts of cis-2-butene-1,4-dial are in agreement with the experimental observations.     

Heterometallic Co(III)(4)Fe(III)(2) Schiff Base Complex: Structure, Electron Paramagnetic Resonance, and Alkane Oxidation Catalytic Activity

The heterometallic complex [Co(4)Fe(2)OSae(8)]·4DMF·H(2)O (1) was synthesized by one-pot reaction of cobalt powder with iron chloride in a dimethylformamide solution of salicylidene-2-ethanolamine (H(2)Sae) and characterized by single crystal X-ray diffraction analysis, magnetic measurements, high frequency electron paramagnetic resonance (HF-EPR), and M?ssbauer spectroscopies. The exchange coupling in the Fe(III)-Fe(III) pair is of antiferromagnetic behavior with J/hc = -190 cm(-1). The HF-EPR spectra reveal an unusual pattern with a hardly detectable triplet signal of the Fe(III) dimer. The magnitude of D (ca. 13.9 cm(-1)) was found to be much larger than in related dimers. The catalytic investigations disclosed an outstanding activity of 1 toward oxidation of cycloalkanes with hydrogen peroxide, under mild conditions. The most efficient system showed a turnover number (TON) of 3.57 × 10(3) with the concomitant overall yield of 26% for cyclohexane, and 2.28 × 10(3)/46%, respectively, for cyclooctane. A remarkable turnover frequency (TOF) of 1.12 × 10(4) h(-1) (the highest initial rate W(0) = 3.5 × 10(-4) M s(-1)) was achieved in oxidation of cyclohexane. Kinetic experiments and selectivity parameters led to the conclusion that hydroxyl radicals are active (attacking C-H bonds) species. Kinetic and electrospray ionization mass spectrometry (ESI-MS) data allowed us to assume that the trinuclear heterometallic particle [Co(2)Fe(Sae)(4)](+), originated from 1 in solution, could be responsible for efficient generation of hydroxyl radicals from hydrogen peroxide.     

On Reduction of Quaternionic Polynomials and Their Identical Equality

We show that any quaternionic polynomial with one variable can be represented in such a way that the number of its terms will be not larger than a certain number depending on the degree of the polynomial. We study also some particular cases where this number can be made even smaller. Then we use the above-mentioned representation to study how to check whether two given quaternionic polynomials with one variable are identically equal. We solve this problem for all linear polynomials and for some types of nonlinear polynomials.     

Tetrahydrofuran lignans via tandem oxidative anionic-radical processes or reductive radical cyclizations

Several tetrahydrofuran lignans have become important due to their diverse biological activities. We present initial studies on short syntheses of some of the simplest members of this natural product class. Galgravin and Veraguensin are obtained in only three or four steps from nitroalkenes and allylic alcohols via a new tandem anionic-radical process, and reductive radical cyclizations of beta-nitro ethers derived from the same precursors are suitable to obtain Galgravin as well as Galbelgin and Ganschisandrin.