Generally, cage‐shaped hosts for saccharides can bind strongly to guest molecules because of the three‐dimensional preorganized hydrogen‐bonding sites. However, the preparation of cage molecules is often difficult because of the low yield of the macrocyclization step. Here, we report a three‐arm‐shaped molecule possessing pyridine‐acetylene‐phenol units as a new kind of host having a preorganized three‐dimensional hydrogen‐bonding site. This three‐arm‐shaped host was readily prepared compared to a cage‐shaped analogue. This host associated with lipophilic glycosides to form chiral complexes, and the association constants were sufficiently high as to be comparable to those of the cage‐shaped analogue. Furthermore, this host extracted native monosaccharides into a lipophilic solvent.

Coordination cages were composed by self-organization of rigid C-symmetric heptaarene tridentates and Pd(II) precursors. The heptaarene framework involves one mesitylene, three phenol, and three pyridine moieties, which were connected by Suzuki coupling reactions. The treatment of the tridentates with Pd(dppp)(OTf) or Pd(en)(NO) in a 2:3 molar ratio furnished coordination cages, which was ascertained by crystallography, H NMR and DOSY measurements, and ESI-TOFMS and UV-vis spectra. The cages have six phenolic hydroxy groups inside and were expected to incorporate hydrogen-bonding guest molecules such as saccharides. CD and DOSY measurements showed that octyl hexoside guests could be incorporated into the cage.