Total Synthesis of Cinnamodial-Based Dimer (-)-Capsicodendrin.

We describe the first total synthesis of cinnamodial-based dimer (-)-capsicodendrin. First, we developed a 12-step synthetic route to access (-)-cinnamodial from 1-vinyl-2,6,6-trimethylcyclohexene. We then showed that (-)-cinnamodial can selectively dimerize to (-)-capsicodendrin under kinetically controlled basic conditions. Our observations regarding a facile conversion of (-)-capsicodendrin back to (-)-cinnamodial hint at the possibility that (-)-capsicodendrin is a chemical reservoir of insecticidal (-)-cinnamodial and Cinnamosma genus plants release it upon environmental stresses.