A computational journey in organoboron chemistry: from photochemistry to cross-coupling catalysis

Organoboron chemistry is one of the most powerful tools in organic synthesis to achieve chemical complexity. In the recent years, boron substituents have been used to modulate the selectivity of chemical reactions. However, the understanding or boron effects is usually a challenging task and requires intensive mechanistic investigations.Along the last years, our group have focused on the computational investigation of different reactions where boron plays a key role in controlling the overall reactivity of the system. Herein, we provide a comprehensive scenario of those effects using four different examples where boron controlsthe outcome of the process. First, we will discuss the chemoselective reduction of carboxylic acids over ketones due to a highly activate organoboron species that is formed by hidden borane chemistry (Figure 1A).[1] Then, a modular access to the counter-thermodynamic disubstituted cyclohexanes will be rationalized based on a cascade reaction where boron plays a key role to revert the thermodynamic driving force (Figure 1B).[2] Finally, the mechanism of two different light-mediated reactions, where boron plays a key role in both the activation and the stability of the resulting radicals (Figure 1C-D), will be briefly introduced to show the amazing potential of boron in radical based photochemistry to modulate the selectivity and the reactivity of metalloid radicals.[3,4]