Expanding Rh-Catalyed Nucleophile Additions to Electron-Deficient Dienes

Abstract

The metal-catalyzed addition of nucleophiles to electron-deficient alkenes represents one of the most useful tools for the construction of carbon-carbon and carbon-heteroatom bonds. Of the methods that have been developed, the Rh-catalyzed conjugate addition of aryl and alkenyl boronic acids to electron-deficient dienes is considered one of the most useful platforms for installing a stereocenter b to an electron-withdrawing group. While this area has seen a tremendous amount of development over the last 25 years, the Rh-catalyzed addition to structurally related electron-deficient dienes remains comparatively underdeveloped. This thesis describes the development of new methods for the stereoselective functionalization of electron-deficient dienes, initiated by nucleophilic addition to the d-position of the diene.