title: A supramolecular microenvironment strategy for transition metal catalysis.
abstract: 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 (k(cat)/k(uncat)) up to 1.9 × 10(7) (here k(cat) and k(uncat) 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.
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA.
authors.forename: David M
authors.initials: DM
authors.lastname: Kaphan
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA.
authors.forename: Mark D
authors.initials: MD
authors.lastname: Levin
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA. rbergman@berkeley.edu raymond@socrates.berkeley.edu fdtoste@berkeley.edu.
authors.forename: Robert G
authors.initials: RG
authors.lastname: Bergman
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA. rbergman@berkeley.edu raymond@socrates.berkeley.edu fdtoste@berkeley.edu.
authors.forename: Kenneth N
authors.initials: KN
authors.lastname: Raymond
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA. rbergman@berkeley.edu raymond@socrates.berkeley.edu fdtoste@berkeley.edu.
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste