Chemo-, regio-, and enantioselective Pd-catalyzed allylic alkylation of indolocarbazole pro-aglycons

[reaction: see text] Monosubstituted isomerically pure indolopyrrolocarbazole precursors have been prepared via palladium-catalyzed asymmetric allylic alkylation methodology, employing both achiral cyclopentenyl electrophiles and chiral glycal derivatives. Chemoselective allylation of (bis)indole lactam pro-aglycon 3 allows access to N-distally substituted indolopyrrolocarbazole derivatives; glyoxamide precursor 14 provides entry into N-proximally substituted derivatives.     

Perturbation Analysis for the Eigenvalue Problem of a Formal Product of Matrices

We study the perturbation theory for the eigenvalue problem of a formal matrix product A ₁ ^{s 1} ··· A _p ^{s p}, where all A _k are square and s _k {–1, 1}. We generalize the classical perturbation results for matrices and matrix pencils to perturbation results for generalized deflating subspaces and eigenvalues of such formal matrix products. As an application we then extend the structured perturbation theory for the eigenvalue problem of Hamiltonian matrices to Hamiltonian/skew-Hamiltonian pencils.     

Exchangelike effects for closed-shell adsorbates: interface dipole and work function

Based on detailed theoretical analyses, we present, for the first time, direct evidence that the significant interface dipole commonly observed for atoms and molecules physisorbed on metal surfaces originates from exchangelike effects. In the case of Xe, previously proposed contributions from chemical interactions do not play a significant role.     

Tuning high-power laser diodes with as much as 0.38 W of power and M(2) = 1.2 over a range of 32 nm with 3-GHz bandwidth

Gain-guided diode lasers usually have emission wavelengths determined by the manufacturing process, with typically 0.5-1-nm bandwidth. Furthermore, their beam quality is rather poor. We show that external cavities allow for tunable narrow-bandwidth operation of gain-guided diode lasers. At the same time the beam quality is drastically improved; almost diffraction-limited light of more than 200 mW has been achieved over the whole tuning range from 910 to 942 nm with narrow bandwidth.     

Very Large Cyclic Compounds

Very large ring systems, containing more than 50 ring members, are becoming increasingly important in different topics in natural sciences. These so-called gigantocycles differ from smaller macrocycles in physical properties, special structural features and chemical behaviour. This article is meant to be the first summary of such ring systems and a synopsis of the most remarkable examples with their fascinating nano-scaled structures and ingenious synthesis. To restrict the scope of the article, only isolated and completely characterized, monodisperse compounds are presented. Furthermore, attention is mainly directed at organic gigantocycles. Some ultracycles with more than 100 ring members, mainly occurring in polymer chemistry and nature, will also be described.     

A fully automatic method for predicting internal reacting flows

A fully automatic method for computing elliptic internal reacting flows is presented. It uses a majorant operator-splitting method for the conservation of species equations, which permits their usually problematic integration to be performed in a two-step process. For the first nonreacting stage the algorithm of Gosman et al. [18] is utilised, whilst the form of the second reacting stage enables the method of characteristics to be implemented so that a set of ordinary differential equations is obtained. The latter are solved using Gear's [5] method for combatting the stiffness that is frequently associated with problems involving realistic chemical kinetic schemes. Some sample results for turbulent reacting flow in a combustor with a conical burner tunnel section demonstrate the viability of the technique.