Details

Autor(en) / Beteiligte

• Kaphan, David M.
• Levin, Mark D.
• Bergman, Robert G.
• Raymond, Kenneth N.
• Toste, F. Dean

Titel

A supramolecular microenvironment strategy for transition metal catalysis

Ist Teil von

• Science (American Association for the Advancement of Science), 2015-12, Vol.350 (6265), p.1235-1238

Ort / Verlag

United States: American Association for the Advancement of Science

Erscheinungsjahr

2015

Quelle

Science (periodical)

Beschreibungen/Notizen

• 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.