title: Triggering activity of catalytic rod-like supramolecular polymers.
abstract: Supramolecular polymers based on benzene-1,3,5-tricarboxamides (BTAs) functionalized with an L- or D-proline moiety display high catalytic activity towards aldol reactions in water. High turnover frequencies (TOF) of up to 27×10(-4) s(-1) and excellent stereoselectivities (up to 96% de, up to 99% ee) were observed. In addition, the catalyst could be reused and remained active at catalyst loadings and substrate concentrations as low as 0.1 mol % and 50 mM, respectively. A temperature-induced conformational change in the supramolecular polymer triggers the high activity of the catalyst. The supramolecular polymer's helical sense in combination with the configuration of the proline (L- or D-) is responsible for the observed selectivity.
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands).
authors.forename: Elisa
authors.initials: E
authors.lastname: Huerta
authors.forename: Bas
authors.initials: B
authors.lastname: van Genabeek
authors.forename: Brigitte A G
authors.initials: BA
authors.lastname: Lamers
authors.forename: Marcel M E
authors.initials: MM
authors.lastname: Koenigs
authors.forename: E W
authors.initials: EW
authors.lastname: Meijer
authors.forename: Anja R A
authors.initials: AR
authors.lastname: Palmans
mesh_terms: D001549:Benzamides / Q000737:chemistry*; D002384:Catalysis; D039301:Computers, Molecular; D046911:Macromolecular Substances / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D011392:Proline / Q000737:chemistry*
chemical_list: D001549:Benzamides; D046911:Macromolecular Substances; D011108:Polymers; C558700:benzene-1,3,5-tricarboxamide; D011392:Proline
keywords: aldol reaction; organocatalysis; proline; self-assembly; supramolecular polymers