DYNAMIC STEREOCHEMISTRY OF SYMMETRICALLY BUT DIFFERENTLY SUBSTITUTED DIPHOSPHANES

Abstract

The main interest of our work in Bonn during the last years was in the field of phosphorus-carbon compounds with multiple bonds. Beside the synthesis of new classes of compounds we were particularly interested in the amazing analogy between the PC- and the CC-double bond, which could be proved by evidence of E/Z isomers and a clear indication of pericyclic reactions.     

MOVIPAC: Vibrational spectroscopy with a robust meta‐program for massively parallel standard and inverse calculations

We present the software package MO VI PAC for calculations of vibrational spectra, namely infrared, Raman, and Raman Optical Activity (ROA) spectra, in a massively parallelized fashion. MO VI PAC unites the latest versions of the programs SNF and AKIRA alongside with a range of helpful add‐ons to analyze and interpret the data obtained in the calculations. With its efficient parallelization and meta‐program design, MO VI PAC focuses in particular on the calculation of vibrational spectra of very large molecules containing on the order of a hundred atoms. For this purpose, it also offers different subsystem approaches such as Mode‐ and Intensity‐Tracking to selectively calculate specific features of the full spectrum. Furthermore, an approximation to the entire spectrum can be obtained using the Cartesian Tensor Transfer Method. We illustrate these capabilities using the example of a large π‐helix consisting of 20 (S)‐alanine residues. In particular, we investigate the ROA spectrum of this structure and compare it to the spectra of α‐ and 3₁₀‐helical analogs. © 2012 Wiley Periodicals, Inc.     

Engyodontochones,Antibiotic Polyketides from the Marine Fungus Engyodontium album Strain LF069

Six new ( 2 , 4 – 8 ) and two known polyketides with a basic structure of an anthraquinone‐xanthone were isolated from mycelia and culture broth of the fungus Engyodontium album strain LF069. The structures and relative configurations of these compounds were established by spectroscopic means, and their absolute configurations were defined mainly by comparison of quantum chemical TDDFT calculated and experimental ECD spectra. Compounds 2 and 4 – 8 were given the trivial names engyodontochone A ( 2 ) and B–F ( 4 – 8 ). Compounds 5 – 8 represent the first example of a 23,28 seco‐beticolin carbon skeleton. The relative and absolute configurations of two known substances JBIR‐97/98 ( 1 ) and JBIR‐99 ( 3 ) were determined for the first time. All isolated compounds were subjected to bioactivity assays. Compounds 1 – 4 exhibited inhibitory activity against methicillin‐resistant Staphylococcus aureus (MRSA) that was 10‐fold stronger than chloramphenicol.     

Traveling Salesman Problem with Clustering

In the original traveling salesman problem, the traveling salesman has the task to find the shortest closed tour through a proposed set of nodes, touching each node exactly once and returning to the initial node at the end. For the sake of the tour length to be minimized, nodes close to each other might not be visited one after the other but separated in the tour. However, for some practical applications, it is useful to group nodes to clusters, such that all nodes of a cluster are visited contiguously. Here we present an approach which leads to an automatic clustering with a clustering parameter governing the sizes of the clusters.