The confined chemical environment of a supramolecular nanovessel can act as a catalyst to promote reactivity that is inaccessible in traditional solution-phase catalysis. This results in an enzyme-like mechanism involving the specific and selective recognition of transition states within the cavity of the vessel. An M4L6 metal-ligand supramolecular cluster was found to promote an aza-Prins cyclization that features a long-range transannular hydride transfer due to the constrictive binding of the cluster cavity, that is unobserved in bulk solution.1 Similarly, a nucleophilic substitution reaction is catalyzed by the cluster, in which remarkable stereochemical retention was observed via a putative cation-π interaction with the electron rich walls of the cluster.2 Finally, the cluster is capable of catalytically promoting carbon-carbon bond forming reductive elimination by intercepting high valent cationic intermediates, which was implemented in a dual catalytic platinum catalyzed cross coupling reaction. 3 Rate enhancements of more than 10 million were observed. These results and others demonstrate the growing complexity and control in supramolecular catalysis. 1 Kaphan, D.; Toste, F. D.; Bergman, R. G.; Raymond, K. N. J. Am. Chem. Soc. 2015, 137, 9202-9205. 2 Zhao, C.; Toste, F. D.; Raymond, K. N.; Bergman, R. G. J. Am. Chem. Soc. 2014, 136, 14409-14412. 3 Kaphan, D.; Levin, M. D.; Bergman, R. G.; Raymond, K. N.; Toste, F. D. submitted for publication.

Enzyme-like catalysis in a chiral supramolecular cluster

251st National Meeting (2016)

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