The stereochemistry of the structurally unique myxobacterial polyketides tuscolid/tuscorons was determined by ac ombination of high-field NMR studies,m olecular modeling,a nd chemical derivatization and confirmed by am odular total synthesis of tuscorons Da nd E. Together with the discovery of three novel tuscorons,this study provides detailed insight into the chemically unprecedented tuscolid/ tuscoron rearrangement cascade.

The stereochemistry of the structurally unique myxobacterial polyketides tuscolid/tuscorons was determined by ac ombination of high-field NMR studies,m olecular modeling,a nd chemical derivatization and confirmed by am odular total synthesis of tuscorons Da nd E. Together with the discovery of three novel tuscorons,this study provides detailed insight into the chemically unprecedented tuscolid/ tuscoron rearrangement cascade.