Asymmetric catalysis at the mesoscale: Gold nanoclusters embedded in chiral self-assembled monolayer as heterogeneous catalyst for asymmetric reactions

Elad Gross, Jack H. Liu, Selim Alayoglu, Matthew A. Marcus, Sirine C. Fakra, F. Dean Toste*, Gabor A. Somorjai

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

139 Scopus citations

Abstract

Research to develop highly versatile, chiral, heterogeneous catalysts for asymmetric organic transformations, without quenching the catalytic reactivity, has met with limited success. While chiral supramolecular structures, connected by weak bonds, are highly active for homogeneous asymmetric catalysis, their application in heterogeneous catalysis is rare. In this work, asymmetric catalyst was prepared by encapsulating metallic nanoclusters in chiral self-assembled monolayer (SAM), immobilized on mesoporous SiO2 support. Using olefin cyclopropanation as an example, it was demonstrated that by controlling the SAM properties, asymmetric reactions can be catalyzed by Au clusters embedded in chiral SAM. Up to 50% enantioselectivity with high diastereoselectivity were obtained while employing Au nanoclusters coated with SAM peptides as heterogeneous catalyst for the formation of cyclopropane- containing products. Spectroscopic measurements correlated the improved enantioselectivity with the formation of a hydrogen-bonding network in the chiral SAM. These results demonstrate the synergetic effect of the catalytically active metallic sites and the surrounding chiral SAM for the formation of a mesoscale enantioselective catalyst.

Original languageAmerican English
Pages (from-to)3881-3886
Number of pages6
JournalJournal of the American Chemical Society
Volume135
Issue number10
DOIs
StatePublished - 13 Mar 2013
Externally publishedYes

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