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Urea‐Functionalized Fe 4 L 6 Cages for Supramolecular Gold Catalyst Encapsulation to Control Substrate Activation Modes
Ist Teil von
Angewandte Chemie, 2023-11, Vol.135 (45)
Erscheinungsjahr
2023
Quelle
Wiley-Blackwell Journals
Beschreibungen/Notizen
Abstract
The excellent catalytic performances of enzymes in terms of activity and selectivity are an inspiration for synthetic chemists and this has resulted in the development of synthetic containers for supramolecular catalysis. In such containers the local environment and pre‐organization of catalysts and substrates leads to control of the activity and selectivity of the catalyst. Herein we report a supramolecular strategy to encapsulate single catalysts in a urea‐functionalized Fe
4
L
6
cage, which can co‐encapsulate a functionalized urea substrate through hydrogen bonding. Distinguished selectivity is obtained, imposed by the cage as site isolation only allows catalysis through π activation of the substrate and as a result the selectivity is independent of catalyst concentration. The encapsulated catalyst is more active than the free analogue, an effect that can be ascribed to transitionstate stabilization rather than substrate pre‐organization, as revealed by the MM kinetic data. The simple strategy reported here is expected to be of general use in many reactions, for which the catalyst can be functionalized with a sulfonate group required for encapsulation.