Chen C.-YXu H.-CHo T.-HHsu C.-JLai C.-CLiu Y.-HPeng S.-MSHENG-HSIEN CHIU2022-04-252022-04-25202100223263https://www.scopus.com/inward/record.uri?eid=2-s2.0-85115917430&doi=10.1021%2facs.joc.1c01580&partnerID=40&md5=9cb02a05c94f7b7113e0e6db0f911d3bhttps://scholars.lib.ntu.edu.tw/handle/123456789/606938In this study we found that 2,6-dimethanolpyridine displays good complementarity toward di(ethylene glycol) for the complexation of Na+ ions, allowing us to use this recognition system for the efficient synthesis of hetero[2]catenanes; indeed, it allowed us to attach multiple copies of [2]catenanes to branched systems presenting multiple isophthalaldehyde units. When we attempted to form a catenane from a preformed macrocycle featuring only a single di(ethylene glycol) unit, reacting it with a di(ethylene glycol) derivative presenting two amino termini, isophthalaldehyde, and templating Na+ ions [i.e., with the aim of using di(ethylene glycol)·Na+·di(ethylene glycol) recognition to template the formation of the interlocked imino macrocycle], the yields of the hetero[2]catenane and homo[2]catenane, comprising two imino macrocyclic units, were both poor (14% and 7%, respectively). In contrast, when one or two 2,6-dimethanolpyridine units were present in the preformed macrocycles, their reactions with the same diamine, dialdehyde, and Na+ ions provided the hetero[2]catenanes with high selectivity and efficiency (44% and 64% yields, respectively), with minimal formation of the competing homo[2]catenane. The high complementary of the 2,6-dimethanolpyridine·Na+·di(ethylene glycol) ligand pair allowed us to synthesize [2]catenane dimers and trimers directly from corresponding isophthalaldehyde-presenting cores, with yields, after subsequent reduction and methylation, of 42% and 31%, respectively. ? 2021 American Chemical Society.AlkylationAminesDimersEthyleneEthylene glycolIonsBranched systemCatenanesEfficient synthesisGlycol derivativesGlycol unitsIsophthalaldehydesMacrocyclesNa+ ionsRecognition systems[2]catenanesPolyols[SDGs]SDG1[SDGs]SDG3journal article10.1021/acs.joc.1c015802-s2.0-85115917430