Rearrangement of a Tricyclic 2,5-Cyclohexadienone: Towards a General Synthetic Route to the Daphnanes and (+)-Resiniferatoxin.

Light as a reagent: A highly functionalized structure that serves as a daphnane template can be formed by the photorearrangement of a 2,5-cyclohexadienone subunit within a complex tricyclic ring system. The chemistry we describe should not only find use in the total synthesis of resiniferatoxin and related daphnanes, but should also provide useful templates for access to complex analogues.