Synthesis of Highly Functionalized Cyclohexenone Rings: Rhodium-Catalyzed 1,3-Acyloxy Migration and Subsequent [5+1] Cy cloaddition

摘要

The Diels-Alder cycloaddition represents the most powerful technology for the preparation of substituted cyclohexenes and has proven to be extremely valuable in organic synthesis. However, efficient syntheses of cyclohexenes having diverse substitutions, stereochemistry, and functionalities are still challenging and continue to stimulate the development of novel cycloaddition reactions. We report herein a stereoselective synthesis of highly functionalized cyclohexenones from substituted cyclopropanes through a rhodium-catalyzed 1,3-acyloxy migration and subsequent [5+1] cycloaddition. Given the well-documented strategies for the preparation of optically pure cyclopropanes, this promises to be a versatile method for the synthesis of complex cyclohexenones from cyclopropanes.