A supramolecular approach to an allosteric catalyst

Nathan C. Gianneschi, Paul A. Bertin, Son Binh T. Nguyen, Chad A. Mirkin*, Lev N. Zakharov, Arnold L. Rheingold

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

214 Scopus citations

Abstract

The design and synthesis of a novel, supramolecular allosteric catalyst system, assembled via the weak-link approach, is presented. The catalyst contains two structural Rh(I) centers in thioether- and phosphine-rich hemilabile pockets, and two functional Cr(III) centers bound within salen-based moieties. The catalytic properties of the supramolecular catalyst are compared to those of a Cr(III)-salen monomeric analogue in the context of the asymmetric ring opening of cyclohexene oxide by TMSN3. Allosteric control is afforded via reactions that occur at distal sites which open the macrocyclic cavity and facilitate the catalytic reaction. Kinetic data show a significant rate increase upon opening of the catalyst's flexible macrocyclic cavity and enhanced selectivity and reactivity with respect to the monomeric Cr(III)-salen analogue. The work presented represents a new approach to the construction of abiotic allosteric catalysts.

Original languageEnglish (US)
Pages (from-to)10508-10509
Number of pages2
JournalJournal of the American Chemical Society
Volume125
Issue number35
DOIs
StatePublished - Sep 3 2003

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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