Synthesis and applications of analogues of Tröger's base as molecular tubes, receptor and ligands

Sammanfattning: Tröger’s base was synthesized for the first time in 1887. The molecule is rigid, C2-symmetric and has a 90° angle, forming a chiral hydrophobic pocket. In this thesis, the synthesis of new analogues of Tröger’s base is described. 2- and 3-halo-substituted anilines have for the first time been condensed to Tröger’s base analogues. It has also been shown that anilines without substituents in para-position are capable of forming Tröger’s base analogues in one step. Since halogenated compounds are easy to modify, this means that it is now possible to synthesize many analogues not attainable earlier. The next part of the thesis describes the synthesis of a Tröger’s base analogue that might be capable of self-aggregating into a tube since it has a complementary hydrogen-bond-pattern in both ends. The first turn of a covalent tube has been synthesized using halogenated Tröger's base analogues as starting materials. Through step-wise build-up of the tube, we will have full control of the length of the tube. The tube will be soluble in both hydrophobic solvents and in acidic water-phase. A bis-crown ether analogue of Tröger’s base has been used as a receptor, discriminating between bis-ammonium salts of different lengths by determination of the association constants. The size of the hydrophobic pocket has been investigated by complexation with bis-ammonium salts carrying side-groups of different size. Finally, some analogues of Tröger’s base were synthesized and two of these were investigated as optically active ligands in two asymmetric reactions and managed to induce optical activity in a small degree in the products.