Novel Catalytic Reactions Enabled by Metal-Induced Boronate Rearrangement

Abstract

This dissertation will discuss the development of three methodologies that take advantage of the intrinsic reactivity of organoboron “ate” complex to undergo boronate rearrangement. The first chapter will describe a nickel-catalyzed conjunctive cross-coupling reaction between 9-BBN boranes and aryl halides. This process provides secondary organoboranes enantioselectively from readily available alkenyl starting materials. The second chapter will describe the development of conjunctive cross-coupling between 9-BBN boranes and acyl electrophiles. We will highlight its unique value in the syntheses of β-hydroxyl carbonyls and show that this reaction is complementary to the aldol reaction. In the third and last chapter of this manuscript, we report the conjunctive crosscoupling reaction of simple achiral borylenynes towards the enantio- and diastereoselective synthesis of α-borylallenes, which provides α-allenols upon oxidative workup.