Dynamic Chirality in Nature Chemistry

We have published a paper in Nature Chemistry describing the dynamic inversion of carbon-centred stereochemistry in fluxionally chiral carbon cages. Watch the video below for an animated summary.

We showed that with appropriate substitution patterns, the rapid and reversible Cope rearrangement of barbaralane carbon cages interchanges pairs of enantiomers. The sp3-C stereocentres in their structures are inverted.

Typically, inverting sp3-C stereocentres requires high-energy bond-breaking and bond-making steps through step-wise intermolecular reactions with external reagents. But the barbaralane stereochemistry is intrinsically dynamic. Our paper shows the consequences of this dynamic bonding: the cage adapts its stereochemistry in response to its environment (through covalently attached groups or associated ions); its rearrangements can be stopped, restarted, and slowed down; and it can pass on its dynamic stereochemical properties to chiral-at-metal ions through forming organometallic complexes.

The research was led by group members Aisha Bismillah, Toby Johnson, and Burhan Hussein. Congratulations to all the team!