Toward the Synthesis of Nuphar Sesquiterpene Thioalkaloids: Stereodivergent Rhodium-Catalyzed Synthesis of the Thiolane Subunit.

A stereodivergent approach to the central thiolane subunit of Nuphar sesquiterpene thioalkaloids has been developed. This approach features a rhodium-catalyzed Stevens-type rearrangement in conjunction with an enzyme resolution reaction. Further elaboration into a polycyclic ring system via alcohol oxidation and ring-closing metathesis is also described.