Self-sorting at interfaces is one of the big challenges we face to prepare the functional organic materials of the future. As a first and decisive step to self-sorting into π-stacks or bundles, we here elaborate self-sorting of π-dimers in solution. Design, synthesis and study of planar naphthalenediimides (NDIs) with one shielded and one free chiral π-surface to direct self-assembly into dimers are described. Stereoisomers are isolated by chiral, preparative HPLC and characterized by X-ray crystallography. NMR studies show that racemates with almost planar, nearly identical π-surfaces prefer uniform self-sorting into homodimers at large differences in π-acidity and alternate self-sorting into heterodimers at small differences in π-acidity. In contrast, enantiomers self-sort “narcissistically” into heterodimers and diastereomers show moderate preference for homodimers. Whereas the lessons learned from dimerization are directly applicable to self-sorting of π-stacks on surfaces, anion transport in lipid bilayers is shown to require a more subtle, somewhat inverse interpretation, with diastereomeric transporters differing dramatically in activity but the least visible supramolecule being confirmed as the best performer

Novel endo,endo-2,5-diaminonorbonane-derived tertiary C2-symmetrical diamines were synthesized via the one-pot reductive amination of enantiomerically pure norbornane-2,5-dione. These ligands were applied to various catalytic reactions such as asymmetric deprotonation, asymmetric bromine-lithium exchange, and enantioselective addition of aryl- and allkylithium reagents to aromatic aldimines

Keywords: Tautomerism / Rhodium / Hydrogenation / Phosphorus / Chirality P-chirogenic, supramolecular hydrogen-bonding C 1 -symmetrical sulfonamido-phosphinamides (METAMORPhos) have been successfully prepared. They were all found to possess a characteristic prototropic equilibrium between the P III and the P V tautomers that is slow on the NMR spectroscopic timescale. Despite the dynamic and reversible protonation of the P centre, the P-chirogenic information was found to be retained in the tautomerization process, even in a protic sol-

The Ir‐catalyzed conversion of prochiral tert‐cyclobutanols to β‐methyl‐substituted ketones proceeds under comparably mild conditions in toluene (45–110 °C) and is particularly suited for the enantioselective desymmetrization of β‐oxy‐substituted substrates to give products with a quaternary chirality center with up to 95 % ee using DTBM‐SegPhos as a chiral ligand. Deuteration experiments and kinetic isotope effect measurements revealed major mechanistic differences to related RhI‐catalyzed transformations. Supported by DFT calculations we propose the initial formation of an IrIII hydride intermediate, which then undergoes a β‐C elimination (C−C bond activation) prior to reductive C−H elimination. The computational model also allows the prediction of the stereochemical outcome. The Ir‐catalyzed cyclobutanol cleavage is broadly applicable but fails for substrates bearing strongly coordinating groups. The method is of particular value for the stereo‐controlled synthesis of substituted chromanes related to the tocopherols and other natural products.