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FULL PAPER DOI: 10.1002/ejoc.201000505 27- to 39-Membered Pyridine Macrocycles Ulrich Lüning,*[a] Ellen Mak,[a] Melanie Zindler,[a] Britta Hartkopf,[a] and Rainer Herges[a] Keywords: Combinatorial chemistry / Macrocycles / Metathesis / Nitrogen heterocycles A set of 27- to 39-membered pyridine macrocycles 2 and 3 low endo interactions. In addition to the length, also the has been synthesized by Williamson ether synthesis or ring- nature of the aliphatic chain was varied: saturated (2) and closing metathesis. The pyridines are 2,6-disubstituted to al- unsaturated (3). Introduction Supramolecules and molecules differ in their mode of binding, but besides the covalent bonds in “ordinary” mole- cules and the supramolecular ion–dipole, π–π binding, or hydrogen-bonding interactions in “ordinary” supramolec- ules, a subclass of supramolecules exists, in which the frag- ments are held together only mechanically: the rotaxanes and catenanes. First only perceived as an exotic class of molecules,[1] the interest in molecular machines[2] has drawn attention to catenanes and rotaxanes.[3] While catenanes are mechanically interlocked, a stable rotaxane is only obtained if the stoppers at either end of the axis are large enough to prohibit a dethreading of the axis. If such a process takes place, the supramolecules are called pseudorotaxanes. Therefore, the size of the ring must be adjusted to the size groups of the rotaxane. Studying polymethylene macro- of the stopper. cycles of ring sizes from 14 to 42, it was shown[5] that For interaction with the axis, the macrocyclic ring must macrocycles larger than 29 may slip on and off the axis. possess respective g