2025/06/01 by Jiankang Zhong, Enzo Olivieri, Patrick Zwick +6 · 2 voices
Chemistry · #Catalytic Cross-Coupling Reactions #Supramolecular Chemistry and Complexes #Synthetic Organic Chemistry Methods
paper · pdf · doi:10.1002/anov.70004
Abstract We report a strategy for catenane synthesis that does not require persistent strong binding interactions on the components nor the addition of templates. The kinetically controlled process features the condensation of a diamine and a p ‐nitrophenol diester accelerated through the cavity of a crown ether. Amidation first generates a linear monoamide bearing an amine at one terminus of the chain and a p ‐nitrophenol ester at the other. This intermediate undergoes macrocyclization via a second amidation reaction through the crown ether cavity, resulting in interlocked macrocycles. Carrying out a similar macrocyclization reaction via ring‐closing alkene metathesis (which is not accelerated through the crown ether cavity) affords macrocycle but no catenane, demonstrating that the metal‐free active template synthesis enables the synthesis of catenanes despite the absence of strong intercomponent binding. A series of catenanes were synthesized in yields of up to 77%. X‐Ray crystallography shows networks of weak intercomponent amide–ether hydrogen bonds in the catenanes, a rarely observed interaction adopted as a result of mechanical interlocking trapping the functional groups in close proximity.