by David M. Kaphan, Mark D. Levin, Robert G. Bergman, Kenneth N

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A supramolecular microenvironment strategy for transition metal catalysis by David M. Kaphan, Mark D. Levin, Robert G. Bergman, Kenneth N. Raymond, and F. Dean Toste Science Volume 350(6265):1235-1238 December 4, 2015 Published by AAAS

Fig. 1 Supramolecular catalysis of reactivity at a transition metal center. Supramolecular catalysis of reactivity at a transition metal center. (A) Structure of the Ga4L6 catalyst. (B) Catalyzed reductive elimination from gold and halide series. Me, methyl; kobs, observed rate; krel, relative rate. (C) Improved catalysis with a triethylphosphine analog. TON, turnover number. (D) Catalyzed reductive elimination from platinum. (E) Identification of a catalyst-deactivation pathway. David M. Kaphan et al. Science 2015;350:1235-1238 Published by AAAS

Fig. 2 Kinetic experiments and implications. Kinetic experiments and implications. (A) Determination of the order in each reactant in the rate law. (B) Proposed mechanism for catalysis by 1. M, metal; X, halide. (C) Experimentally determined rate law. (D) Measured values for kcat and overall acceleration. Asterisks denote 298 K in MeOH-d4; the dagger symbol indicates 313 K in 9:1 MeOH-d4/D2O. (E) Lineweaver-Burk analysis. All error bars represent 1 SD, based on three replicates. David M. Kaphan et al. Science 2015;350:1235-1238 Published by AAAS

Fig. 3 Demonstration of dual catalysis. Demonstration of dual catalysis. (A) Modified supramolecular assembly with improved stability to electrophiles. (B) Dual catalytic alkyl-alkyl cross-coupling enabled via supramolecular catalysis. (C) Proposed mechanism. David M. Kaphan et al. Science 2015;350:1235-1238 Published by AAAS