En Route to Synthetic Phosphodiesterases: Supramolecular Phosphoryl‐Transfer Mediated by Amidinium–Phosphate Contact Ion‐Pairs

Abstract

Proximity effects and electrophilic activation combined account for the accelerated ring-opening in the transesterification of 1 with amidinium alcohol 2. The spatial proximity effects arise in a contact ion-pair of 1 and 2. Electrophilic activation causes the 9000-fold rate enhancement of the reaction of 1 with 2 relative to the reaction with phenylalcohol; the addition of 2 to the transesterification of 1 with phenyl alcohol to form 3 caused a 25-fold rate increase.