Creating Dynamic Nanospaces in Solution by Cationic Cages as Multirole Catalytic Platform for Unconventional C(sp)−H Activation Beyond Enzyme Mimics.

Herein we demonstrate that, based on the creation of dynamic nanospaces in solution by highly charged positive coordination cage of [Pd6(RuL3)8]28+, multirole and multi‐way cage‐confined catalysis is accomplishable for versatile functions and anomalous reactivities with the aid of the biomimetic cage effect. The high cationic‐host charges drive partial deprotonation of 24 imidazole‐NHs on cage sphere alike imidazole‐residuals in proteins, generating amphoteric heterogeneity in solution to enforce effective cavity‐basicity against solution‐acidity. Synergistic actions arisen from cage hydrophobicity, host‐guest electrostatic interactions and imidazole‐N coordination facilitate C(sp)−H activation and carbanionic intermediate stabilization of terminal alkynes to achieve unusual H/D‐exchange and Glaser coupling under acidic conditions, and enable phase transfers of water‐insoluble substrates/products/co‐catalysts to make immiscible‐phase and bi‐phase catalysis feasible, thus providing a useful catalytic protocol to combine merits from homogeneous, heterogeneous, enzymatic and phase transfer catalysis. [ABSTRACT FROM AUTHOR]