We present a simple strategy for the synthesis of main chain oligonucleotide rotaxanes with precise control over the position of the macrocycle. The novel DNA-based rotaxanes were analyzed to assess the effect of the mechanical bond on their properties.
View Article and Find Full Text PDFCatenanes, molecules in which two rings are threaded through one another like links in a chain, can form as two structures related like an object and its mirror image but otherwise identical if the individual rings lack bilateral symmetry. These structures are described as "topologically chiral" because, unlike most chiral molecules, it is not possible to convert one mirror-image form to the other under the rules of mathematical topology. Although intriguing and discussed as early as 1961, to date all methods of accessing molecules containing only this topological stereogenic element require the separation of the mirror-image forms via chiral stationary phase high-performance liquid chromatography, which has limited their investigation to date.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2018
Chiral interlocked molecules in which the mechanical bond provides the sole stereogenic unit are typically produced with no control over the mechanical stereochemistry. Here we report a stereoselective approach to mechanically planar chiral rotaxanes in up to 98:2 d.r.
View Article and Find Full Text PDFWhat has it got in its pockets? A new approach to the selective binding and reporting of stereoisomers using mechanical bonding to produce a well-defined three-dimensional binding pocket was recently reported by Beer and co-workers. The highly stereoselective binding of stereoisomers by the reported [3]rotaxane suggest that the use of the mechanical bond to engineer a binding pocket has great potential for the development of stereoselective hosts.
View Article and Find Full Text PDFAlthough metal-ion-binding interlocked molecules have been under intense investigation for over three decades, their application as scaffolds for the development of sensors for metal ions remains underexplored. In this work, we demonstrate the potential of simple rotaxanes as metal-ion-responsive ligand scaffolds through the development of a proof-of-concept selective sensor for Zn .
View Article and Find Full Text PDFWe report a rotaxane based on a simple urea motif that binds Cl selectively as a separated ion pair with H and reports the anion binding event through a fluorescence switch-on response. The host selectively binds Cl over more basic anions, which deprotonate the framework, and less basic anions, which bind more weakly. The mechanical bond also imparts size selectivity to the ditopic host.
View Article and Find Full Text PDFThe catalyst palladium/2,9-CD3-phenanthroline has a 1.8 times higher turnover number than its non-deuterated counterpart in the aerobic alcohol oxidation of methyl glucoside and allows the regioselective oxidation with dioxygen as the terminal oxidant.
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