An inverse electron demand Diels-Alder-based total synthesis of defucogilvocarcin V and some C-8 analogues.

A concise total synthesis of defucogilvocarcin V is reported. The key features of the approach are the formation of the C-ring using a vinylogous Knoevenagel/transesterification reaction and construction of the D-ring by way of an inverse electron demand Diels-Alder-driven domino reaction. The resulting C-8 ester functionality provides a handle for the synthesis of defucogilvocarcin V as well as some C-8 analogues from a common late-stage intermediate.