Organic Chemistry

A Mechanically Planar Chiral Rotaxane Ligand for Enantioselective Catalysis



Rotaxanes are interlocked molecules in which a molecular ring is trapped on a dumbbell-shaped axle due to its inability to escape over the bulky end groups, resulting in a so-called mechanical bond. Interlocked molecules have mainly been studied as components of molecular machines, but the crowded, flexible environment created by threading one molecule through another, reminiscent of the active site of an enzyme, has also been explored in catalysis and sensing. However, so far the applications of one of the most intriguing properties of interlocked molecules, their ability to display stereogenic units that do not rely on the stereochemistry of their covalent subunits, termed "mechanical chirality", have yet to be properly explored and prototypical demonstration of the applications of mechanically chiral rotaxanes remain scarce. Here we describe a mechanically planar chiral rotaxane-based Au complex that mediates a cyclopropanation reaction with stereoselectivities that are comparable with conventional covalent catalyst reported for this reaction.


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Supplementary material

Thumbnail image of ESI Heard Au Catalysis.pdf
ESI Heard Au Catalysis
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Heard Au Catalysis TOC