Stereochemical Control of Skeletal Diversity

Substrates having appendages that pre-encode skeletal information (σ-elements) can be converted into products having distinct skeletons
using a common set of reaction conditions. The sequential use of the Ugi 4CC-IMDA reaction, followed by allylation, hydrolysis, and acylation
of a chiral amino alcohol appendage (σ-element), leads to substrates for a ROM/RCM or RCM reaction. The stereochemistry of the σ-element
and not its constitution controls the outcome of the pathway selected. This work illustrates the potential of linking stereochemical control to
the challenging problem of skeletal diversity.