Stereoselective Assembly of Hydrogen‐Bonded Anionic Cages Dictated by Organophosphate‐Based Chiral Nodes

Organophosphates are critically involved in biological signal transduction, and they can play a similar role in supramolecular systems. Organophosphates have now been utilized as chiral nodes to transfer asymmetry information to hydrogen-bonded anionic cages, with the supramolecular chirality readily modulated by encapsulated achiral guests, temperature, and protonation/deprotonation of the anions.

Abstract

Inspired by the signal transduction function of organophosphates in biological systems, bioactive organophosphates were utilized for the first time as chiral nodes to dictate the stereoselective assembly of hydrogen-bonded anionic cages. Phosphonomycin (antibiotics), tenofovir (antivirals), adenosine monophosphate (natural product, AMP) and clindamycin phosphate (antibiotics) were assembled with an achiral bis-monourea ligand, thereby leading to the stereoselective formation of quadruple or triple helicates. The extent of the stereoselectivity could be enhanced by either lowering the temperature or adding stronger-binding cations as templates. With the chiral anionic cages as the host, some enantioselectivity was achieved when binding chiral quaternary ammonium cations.

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