文摘
Through the combined use of computational (density functional theory) and experimental studies, a new [Rh(CO)<SUB>2Cl]2 catalyzed two-component [5+2+1] cycloaddition of ene-vinylcyclopropanes and CO for the synthesis of fused bicyclic cyclooctenones has been designed and experimentally realized. The key point behind this design is to turn a disfavored reductive elimination of (sp3)C-Rh-C(sp3) to an easier migratory reductive elimination of (sp3)C-Rh-CO-C(sp3) by the introduction of CO. These reactions proceed in good yields for substrates with various tether types and substituents, providing a flexible, convenient, efficient, and stereocontrolled method for the construction of bicyclic cyclooctenones.