Efficient Synthesis of Cyclic Poly(ethylene glycol)s under High Concentration Conditions by the Assistance of Pseudopolyrotaxane with Cyclodextrin Derivatives.

An efficient synthesis of cyclic polymers (CPs) is in high demand due to their unique properties. However, polymer cyclization generally occurs at low concentrations (0.1 g/L), and the synthesis of CPs at high concentrations remains a challenge. Herein an efficient cyclization of poly(ethylene glycol) ( = 2000 g/mol, 4000 g/mol) (PEG-2k, PEG-4k) in high concentration (80 g/L) is realized by the assistance of polyrotaxane (pPRx). Water-soluble pPRx with a U-like-shape inclusion motif is prepared by mixing the 2-hydroxypropyl-γ-cyclodextrin (HPγCD) and PEG with ()-3,4,5-trimethoxycinnamate (, ). Subsequent irradiation of the pPRx solution (10-80 g/L) by UV light gives cyclic polymers through the intramolecular [2 + 2] photocycloaddition of the cinnamoyl moieties. The photoreaction of in the pPRx system gives cyclic monomers () as major products with a yield of 66% at 80 g/L. Additionally, the cyclization of also gives as major products with a yield of 45% at a concentration of 80 g/L.