Rearrangements of the Chrysanthenol Core: Application to a Formal Synthesis of Xishacorene B

Reported here are substrate-dictated rearrangements of chrysanthenol derivatives prepared from verbenone to access complex bicyclic frameworks. These rearrangements set the stage for a 10-step formal synthesis of the natural product xishacorene B. Key steps include an anionic allenol oxy-Cope rearrangement and a Suárez directed C-H functionalization. The success of this work was guided by extensive computational calculations which provided invaluable insight into the reactivity of the chrysanthenol-derived systems, especially in the key oxy-Cope rearrangement.