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Kaphan, David M.; Levin, Mark D.; Bergman, Robert G.; Raymond, Kenneth N.; Toste, F. Dean
Science (American Association for the Advancement of Science), 12/2015, Letnik: 350, Številka: 6265Journal Article
A self-assembled supramolecular complex is reported to catalyze alkyl-alkyl reductive elimination from high-valent transition metal complexes such as gold(III) and platinum(IV), the central bond-forming elementary step in many catalytic processes. The catalytic microenvironment of the supramolecular assembly acts as a functional enzyme mimic, applying the concepts of enzymatic catalysis to a reactivity manifold not represented in biology. Kinetic experiments delineate a Michaelis-Menten-type mechanism, with measured rate accelerations (Kcat/Kuncat)up to 1.9 × 10⁷ (here Kcat and Kuncat are the Michaelis-Menten enzymatic rate constant and observed uncatalyzed rate constant, respectively). This modality has further been incorporated into a dual catalytic cross-coupling reaction, which requires both the supramolecular microenvironment catalyst and the transition metal catalyst operating in concert to achieve efficient turnover.
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in: SICRIS
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