A New Insight into the Stereoelectronic Control of the Pd0-Catalyzed Allylic Substitution: Application for the Synthesis of Multisubstituted Pyran-2-ones via an Unusual 1,3-Transposition

Pyran-2-ones 3 undergo a novel Pd⁰-catalyzed 1,3-rearrangement to afford isomers 6 . The reaction proceeds via an η²-Pd complex, the pyramidalization of which (confirmed by quantum chemistry calculations) offers a favorable antiperiplanar alignment of the Pd−C and allylic C−O bonds ( C ), thus allowing the formation of an η³-Pd intermediate. Subsequent rotation and rate-limiting recombination with the carboxylate arm then gives isomeric pyran-2-ones 6 . The calculated free energies reproduce the observed kinetics semi-quantitatively.     

Some Aspects of Intra- and Inter-Molecular Reactions of Siliconium Ions in the Vapor Phase

Intramolecular rearrangement processes in the mass spectra of trimethylsilyl derivatives of hydroxy steroids are discussed in terms of the reaction of a siliconium center and a heteroatom. The reaction is shown to be stereospecific. The reactivity of siliconium cations also results in the occurrence of intermolecular reactions under electron impact ionization conditions. Tetramethylsilane is used as a precursor for the production of siliconium ions and examples of chemical ionization mass spectra employing this reagent are shown.     

Dynamical versus variational symmetries: understanding Noether's first theorem

It is argued that awareness of the distinction between dynamical and variational symmetries is crucial to understanding the significance of Noether's 1918 work. Special attention is paid, by way of a number of striking examples, to Noether's first theorem, which establishes a correlation between dynamical symmetries and conservation principles.     

The Dynamics of the Reaction of FeO+ and H2: A Model for Inorganic Oxidation

Extensive density functional theory (DFT) calculations using the B3LYP functional were used to explore the sextet and quartet energy potential energy surfaces (PESs) of the title reaction, and as a basis to fit global analytical reactive PESs. Surface-hopping dynamics on these PESs reproduce the experimentally observed reactivity and confirm that hydrogen activation rather than spin-state change is rate-limiting at low reaction energy, where the main products are Fe⁺ and H₂O. A change in spin state is inefficient in the product region so that excited-state ⁴Fe⁺ is the dominant product. At higher energies, spin-allowed hydrogen atom abstraction to form FeOH⁺ predominates. At intermediate energy, a previously unexpected rebound mechanism contributes significantly to the reactivity.     

Chaotic dynamics of resistively coupled DC-driven distinct Josephson junctions and the effects of circuit parameters

Two distinct Josephson junctions (JJs) connected with a constant coupling resistance R_cp are theoretically considered to investigate the overall dynamics below and above the critical current I_c. The circuit model of the device is driven by two DC current sources, I₁ and I₂. Each junction is characterized by a nonlinear resistive–capacitive junction (NRCSJ). Having constructed the circuit model, time-dependent simulations are carried out for a variety of control parameter sets. Common techniques such as bifurcation diagrams, two-dimensional attractors and Lyapunov exponents are applied for the determination of chaotic as well as periodic dynamics of the superconducting junction devices. According to the findings, two states (namely superconducting and ordinary conducting) are determined as functions of the source currents. The chaotic current which flows through R_cp exhibits a very rich behavior depending on the source currents I₁ and I₂ and junction capacitances C₁ and C₂. The device characteristics are summarized by a number of three-dimensional phase diagrams in the parameter space. In addition, for certain parameters, hyper-chaotic cases with two positive Lyapunov exponents are encountered. In contrast to earlier studies claiming the need for a sinusoidal feeding current for generating a chaotic signal, our circuitry can easily generate one via a DC source.     

The Coordination Behaviour of the Peroxodisulfate Anion with Group XII Metal Ions: [Zn(H2O)(C12H8N2)2(S2O8)]·H2O and Related Compounds

Abstract  

The title compound is monomeric with a Zn(II) hexacoordinated center. The coordination sphere is formed by four nitrogens from two phenanthroline molecules, one oxygen from a monodentate peroxodisulfate ion, and one oxygen from a water molecule. A non-coordinated water molecule completes the formula with an important role in the stabilization of the structure through the formation of two O_HW–H···O_pds bridges (acting as a donor) and one O_CW–H···O_HW bridge where it is an acceptor group (HW: hydration water; pds: peroxodisulfato; CW: coordinated water). The compound is triclinic, space group P-1 with a = 8.763 (3) ?, b = 9.068 (3) ?, c = 17.531 (6) ?, α = 96.48 (2)°, β = 103.94 (3)°, γ = 104.57 (3)°, V = 1286.0 (7) ?³ and Z = 2. The structure was solved by direct methods with a conventional R (on F) = 0.050 for 4534 reflections with Fo > 4σ(Fo). The compound is isomorphous with the Cd analogue (in Harvey et al. Aust J Chem 54:307, 2001). An eventual dependence of conformation and coordination mode of the peroxodisulfate anion on the ancillary organic ligand taking part in the coordination compounds analyzed is discussed.     

Solid Phase Synthesis. Evidence for and Quantification of Intra res in Reactions

Abstract

Intrareaction occurs between moieties attached to copolystyrene-2% divinylbenzene resin as used in solid phase synthesis even when only 0.5% of the phenyl residues are functionalized. Evidence for this interaction has been obtained from the dimeric products resulting from Dieckmann cyclization of resin bound sebacates and ω-cyanopelargonyl thiol resin esters, from kinetic and product data on radioactivity scrambling during the Dieckmann cyclization of uniquely singly labeled tertiary alkyl pimeloyl resin esters, and from anhydride formation with carboxymethyl resin. The extent to which site-site interactions can occur as a function of the percentage functionalization has been measured quantitatively by radiotracer studies on intraresin anhydride formation from carboxymethyl substituted resin. The synthesis and characterization of the resin bound re-actants is described, and the significance of these observations is discussed.