Novel antibiotics: second generation macrocyclic peptides designed to trap Holliday junctions

Described are the syntheses of 15 macrocyclic peptides designed to trap Holliday junctions (HJs) in bacteria during site-specific and homologous recombination. This leads to inhibiting bacterial growth. These second generation macrocycles were based on the C-2 symmetrical HJ. They were synthesized using a strategy that permits elucidation of the amino acid role in binding HJs. The syntheses of these macrocycles are an important step in the development of a new class of antibiotics.     

Phospha-palladacycles and N-heterocyclic carbene palladium complexes: efficient catalysts for CC-coupling reactions

Due to the great importance of palladium-catalyzed Heck-type reactions in scientific and industrial chemistry, a lot of publications and reviews have been published during the last years describing this matter under different aspects. This article presents a summary of catalytic applications of palladium complexes with phosphorus ligands containing a metallated sp³-carbon centre (“palladacycles”) or with N-heterocyclic carbene ligands in C-C and C-N coupling reactions of aryl halides including recent results of mechanistic discussions about their role in the catalytic cycle.     

Free radical-mediated vinyl amination: a mild, general pyrrolidinyl enamine synthesis

The complete scope of free radical-mediated vinyl amination is described, using 5-exo-trig cyclizations of vinyl radicals to the nitrogen of azomethines. The focus is primarily on N,N-dialkyl enamines since their nucleophilicity renders them the most challenging enamines to synthesize using redox conditions. These studies establish several encouraging precedents for the broader application of this strategy.     

Solving Sequences of Refined Multistage Stochastic Linear Programs

Multistage stochastic programs with continuous underlying distributions involve the obstacle of high-dimensional integrals where the integrands' values again are given by solutions of stochastic programs. A common solution technique consists of discretizing the support of the original distributions leading to scenario trees and corresponding LPs which are – up to a certain size – easy to solve. In order to improve the accuracy of approximation, successive refinements of the support result in rapidly expanding scenario trees and associated LPs. Hence, the solvability of the multistage stochastic program is limited by the numerical solvability of sequences of such expanding LPs. This work describes an algorithmic technique for solving the large-scale LP of refinement ν based on the solutions at the previous ν?1 refinements. Numerical results are presented for practical problem statements within financial applications demonstrating significant speedup (depending on the size of the LP instances).     

Synthese und Struktur von γ-Halogenpropyl-octa(silasesquioxanen)

Synthesis and Structures of γ-Halopropyl-octa(silasesquioxanes) As a more rapid and versatile synthetic approach, we have studied the FeCl₃-catalyzed hydrolytic polycondensation of suited trichlorosilanes in a biphasic system which yields e.g. the new octa(silasesquioxane) (BrCH₂CH₂CH₂)₈Si₈O₁₂.     

An explicit characterization of Calogero-Moser systems

Combining theorems of Halphen, Floquet, and Picard and a Frobenius type analysis, we characterize rational, meromorphic simply periodic, and elliptic KdV potentials. In particular, we explicitly describe the proper extension of the Airault-McKean-Moser locus associated with these three classes of algebro-geometric solutions of the KdV hierarchy with special emphasis on the case of multiple collisions between the poles of solutions. This solves a problem left open since the mid-1970s.