Domando radicais pela libertação do potencial sintético de bis(silil)peróxidos

The main goal of this project is to explore the utility of bis(silyl)peroxides (BSPs) as the source of sp3-carbon-centered radicals (CCRs) in organic synthesis, by bringing their unexplored reactivity to the spotlight of photoredox catalysis and electrosynthesis. During this project, answers to the following questions are aimed to be clarified: 1) what are the best conditions to promote the homolytic cleavage of bis(silyl)peroxides? 2) can the outcome of the bis(silyl)peroxides cleavage be varied depending on the use of thermolytic, photolytic, or electrolytic conditions? 3) what is the effect of silicon’s substituents on promoting the homolytic cleavage and its impact on the fate of the formed radical species; 4) are bis(silyl)peroxides able to deliver aryl, alkyl, and siloxyl radicals, and their reactivity be harnessed by metal complexes? 5) what are the required electronic features of saturated bonds to undergo reaction with CCRs derived from BSPs homolytic cleavage? The first goal is to prepare some known BSPs and develop new ones to be studied and applied in metal-catalyzed processes, in conjugation with state-of-the-art photoredox catalytic methods. The next goal is focused on studying their reactivity, harnessing the putative radical species formed to functionalize ubiquitous functionalities such as C=C bonds and the modification of N-H bonds of N-heterocycles. The third ultimate goal of this project is the exploitation of siloxyl radicals as a way to functionalize arenes in a late-stage functionalization approach. It is envisioned that the use of photocatalysis will allow chemoselective functionalization, paving the way for another method of obtaining drugs, thus reducing the shortage of simple methods with mild conditions. An ultimate goal of BiSiPe4Tame will be the transposition of the method from batch to continuous flow in order to increase the efficiency of the transformation. While strong evidence from the literature can be found about the use of thermal catalytic conditions for the generation of CCRs from BSPs, it is envisioned that photoredox and electrosynthetic conditions can provide milder conditions for similar transformations or even alter the fate of the reactions. The strengths of such methods will be emphasized with their incorporation with continuous flow systems, thus ultimately validating the suitability, usability, and capacity of BSPs in organic synthesis.