ABSTRACTDISCOVERY AND THE DEVELOPMENT OF BISMUTH SALT MEDIATED CATALYTIC DEBORYLATIONAND ALLIED STUDIESByFangyi ShenArylboronate esters are versatile synthetic building blocks. Iridium catalyzed C–H activation/borylation reactions are a green way of making such building blocks as these reactions often obviate the need for prior functionalization (e.g. halogenation), the use of pyrophoric reagents, cryogenic conditions, etc. Installation of multiple boron substituents about the starting arene and then Ir catalyzed selective deborylation of the individual borons can allow for the formation of an even greater diversity of borylated building blocks.The regioselectivity of Ir-catalyzed borylations is usually driven by sterics, however heterocycles are known to borylated at positions that exihibt heightened C-H acidity through the influence of the heteroatom. The regioselective borylation attained with a tryptophan derivative has been utilized in the development of a novel convergent route to the TMC-95 core. While pursueing a model synthesis of this natural product, the ability of bismuth salts to catalyze deborylations was discovered. These bismuth salts mediated methods can be highly selective in the in the deborylation of di and triborylated indoles. Furthermore bismuths compounds are safe and less expensive as compared to the Ir-catalysts that facilitated deborylation. Numerous screening experiments on both substrates and other metal salts afforded a better understanding of how these novel deborylations can be applied in various synthetic settings and provided insight into possible mechanisms.
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