Construction of the remarkable 11-carbon frame of the antibiotic tunicamycin is shown to use cyclic enol ethers (exo-glycals) — the first time such intermediates have been seen in biology. Exo-glycal synthase TunA uses an elegantly subtle mechanism to control regioselectivity and with exo-glycal epimerase TunF sets a logical chemical stage for downstream radical C–C coupling.
- Filip J. Wyszynski
- Seung Seo Lee
- Benjamin G. Davis
