Michel Rickhaus

Stereoselective Arene-Forming Aldol Condensation: Synthesis of Configurationally Stable Oligo-1,2-naphthylenes.

Structurally well-defined oligomers are fundamental for the functionality of natural molecular systems and key for the design of synthetic counterparts. Herein, we describe a strategy for the efficient synthesis of individual stereoisomers of 1,2-naphthylene oligomers by iterative building block additions and consecutive stereoselective arene-forming aldol condensation reactions. The catalyst-controlled atropoenantioselective and the substrate-controlled atropodiastereoselective aldol condensation reaction provide structurally distinct ter- and quaternaphthalene stereoisomers, which represent configurationally stable analogues of otherwise stereodynamic, helically shaped ortho-phenylenes.

Template-Directed Synthesis of a Conjugated Zinc Porphyrin Nanoball

We report the template-directed synthesis of a π-conjugated 14-porphyrin nanoball. This structure consists of two intersecting nanorings containing six and 10 porphyrin units. Fluorescence upconversion spectroscopy experiments demonstrate that electronic excitation delocalizes over the whole three-dimensional π system in less than 0.3 ps if the nanoball is bound to its templates or over 2 ps if the nanoball is empty.

Single-Acetylene Linked Porphyrin Nanorings

The synthesis of ethyne-linked porphyrin nanorings has been achieved by template-directed Sonogashira coupling. The cyclic hexamer and octamer are predicted by density functional theory to adopt low symmetry conformations, due to dihedral twists between neighboring porphyrin units, but their symmetries are effectively D6h and D8h, respectively, in solution by 1H NMR. The fluorescence spectra indicate that the singlet excited states of these nanorings are highly delocalized.

Determining Inversion Barriers in Atrop- isomers - A Tutorial for Organic Chemists.

Dynamic behavior is a fascinating property of natural and artificial systems and its understanding has significantly impacted the transformation of molecular interchanges into controlled molecular motion. In this tutorial, the key descriptors of enantiomeric stability are examined in-depth. Enantiomerization and racemization are discussed and differentiated on a fundamental level proposing a unified and distinct nomenclature. Their mathematical meanings and relations are described and deduced cohesively in the context of atropisomerization. The calculation of inversion barriers from thermodynamic and kinetic data is demonstrated and the interdependences between the latter are explained mathematically. Using current examples from our group, the determination of rate constants and the thermodynamic parameters is shown in a step-by-step manner using the most common techniques. The tutorial is concluded with aspects and considerations concerning statistical data analysis and error determination of measurements including a practical guide to Monte-Carlo simulations.

Basel Chemistry Symposium 2014 In Memory of Prof. T. Reichstein

The symposium was opened by Prof. Andreas Pfaltz with a short introduction on the impact of Prof. Reichstein on the development of the Chemistry Department and the pharma industry in Basel, including some personal reminiscences from the time when Prof. Reichstein was still active in the department as Emeritus. Christophe Daeppen*, Daniel Bachmann, Andrea Pannwitz, Isabel Kerschgens, Charlotte Laupheimer, Martin Rother, Lukas Jundt, Michel Rickhaus, Markus Gantenbein, and Ina Bodoky