A General Method for High-Pressure-Promoted Postfunctionalization of Unclosed Cryptands: Potential Phase-Transfer Catalysts.

We report a high-pressure approach to facile late-stage functionalization of unclosed cryptands (UCs) (11 examples, yield up to 99%). Direct comparison of classic and high-pressure conditions of the quaternization reaction in a sterically crowded intraannular position is investigated, and differences in the reactivity of tertiary amine substrates are discussed. Finally, we demonstrated the application of UCs as catalysts for synthetically important alkylation reactions under phase-transfer conditions.