A supramolecular microenvironment strategy for transition metal catalysis

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Science  04 Dec 2015:
Vol. 350, Issue 6265, pp. 1235-1238
DOI: 10.1126/science.aad3087

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Faster elimination inside a cavity

Metals are adept at shuffling molecular bonds. They pry apart two atoms and then pair each one with a different partner. Sometimes the atoms get stuck on the metal, though, and the newly partnered products aren't released. Kaphan et al. designed a strategy for accelerating this elimination process (see the Perspective by Yan and Fujita). A hollow supramolecular capsule captured a gold or platinum complex and induced rapid bond formation between the carbon atoms in methyl groups bound to the metal. Generalization of this strategy could open the door to a wide range of chemical transformations that are currently held up by slow eliminations.

Science, this issue p. 1235; see also p. 1165


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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