Metal template synthesis of hard-to-access mechanically interlocked molecules

Abstract

The construction of mechanically interlocked molecules has been the subject of decades of research. The efficiency of strategies for preparing these molecules has increased continuously. In recent years, the transition metal templation strategy has played quite a remarkable role in the synthesis of entwined or mechanically bonded structures due to the metals’ diverse coordination chemistry and ability to chelate ligands. In the early stages of this method’s development, the metal ions were used as integral part of the scaffold for such components as rings and stoppers to generate the interlocked structures. In newly developed active metal templation strategies, metal ions are used to promote covalent bond forming reactions while simultaneously acting as structural supports.

In this thesis, three main aspects are expanded for the discussion of the application of metal template strategies. First of all, the newly developed strategy - active metal template - will be described and exemplified using the Huisgen-Meldal-Fokin Cu(I)- catalyzed 1,3-cycloaddition of azides with terminal alkynes (the CuAAC “click” reaction), the Cu(I)-mediated Cadiot-Chodkiewicz heterocoupling of an alkyne halide with a terminal alkyne, and the Ni(II)-catalyzed Csp3-Csp3 homocoupling reaction.

Secondly, the thesis discusses the use of these strategies to obtain several hard-to-access structures, including the first high-yielding doubly threaded [3]rotaxanes, heterocircuitcatenanes and the one pot synthesis of homocircuit-catenanes, and the smallest molecular trefoil knot prepared to date.

Lastly, as an extension of the metal temptation strategy, the final chapter of this thesis will discuss the assembly of inorganic metal-organic catenanes by metal coordination.