Publication Details (including relevant citation information):
Tisdale, E. J.; Slobodov, I.; Theodorakis, E. A. Unified synthesis of caged Garcinia natural products based on a site‐selective Claisen/Diels-Alder/Claisen rearrangement. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 12030-12035.
A unified synthetic strategy toward caged Garcinia natural products has been designed and implemented. Central to the strategy is a tandem Claisen/Diels-Alder/Claisen rearrangement of a suitably substituted xanthone precursor to form forbesione. Serving as a template, forbesione is then used to deliver representative members of this family, including desoxygaudichaudione A, desoxymorellin, and gambogin. Studies on the timing of this reaction cascade suggest that the C-ring Claisen/Diels-Alder rearrangement proceeds initially and is followed by the A-ring Claisen reaction. The electronic and steric effects that govern the outcome of this cascade are presented.
Address (URL): http://dx.doi.org/10.1073/pnas.0401932101