Total Synthesis of the Quinone Epoxide Dimer (+)-Torreyanic Acid: Application of a Biomimetic Oxidation/Electrocyclization/Diels−Alder Dimerization Cascade<sup>1</sup>
2003-04-03T00:00:00Z (GMT) by
An asymmetric synthesis of the quinone epoxide dimer (+)-torreyanic acid (<b>48</b>) has been accomplished employing [4 + 2] dimerization of diastereomeric 2<i>H</i>-pyran monomers. Synthesis of the related monomeric natural product (+)-ambuic acid (<b>2</b>) has also been achieved which establishes the biosynthetic relationship between these two natural products. A tartrate-mediated nucleophilic epoxidation involving hydroxyl group direction facilitated the asymmetric synthesis of a key chiral quinone monoepoxide intermediate. Thermolysis experiments have also been conducted on a model dimer based on the torreyanic acid core structure and facile retro Diels−Alder reaction processes and equilibration of diastereomeric 2<i>H</i>-pyrans have been observed. Theoretical calculations of Diels−Alder transition states have been performed to evaluate alternative transition states for Diels−Alder dimerization of 2<i>H</i>-pyran quinone epoxide monomers and provide insight into the stereocontrol elements for these reactions.