BETELGEUSE · Transforming Boron Chemistry By Exploring Boryl Radical Reactivity

Our ability to construct organic molecules is central to the wellbeing of our society. Boron-containing compounds are some of the most used tools to aid this. These materials are used as building blocks when “stitching” molecules together and also as catalysts in many different settings. The invention of innovative strategies to prepare and exploit borylated molecules is integral to discover and manufacture many products that we use daily. The overarching aim of this proposal is to innovate organic chemistry by inventing novel catalysis concepts based on the reactivity of boryl radicals, an underutilized class of reactive intermediates. My group has introduced a novel approach to generate these species from amine-borane precursors and here I aim to:1. Establish a general platform to borylate aromatics using boryl radicals. This blueprint for C–B bond formation will introduce amine-borane functionalities instead of standard boronic acids/esters. This will provide unprecedented synthetic capacity because the amine-borane will serve a dual role acting first as directing group for ortho/meta functionalization and then cross-coupling handle.2. Explore boryl radicals in innovative cascades reactions leading to the divergent assembly of sp3-rich fragments. These methods will expedite the preparation of poly-functionalized materials tapping into unexplored areas of chemical space.3. Establish boryl radicals as “H-atom transfer” catalysts to achieve the “philicity umpolung” of nucleophilic radicals. This concept will introduce unprecedented retrosynthetic tactics and enable the merge of boryl radical reactivity with asymmetric organocatalysis. Overall, this cohesive and innovative research plan offers the unique opportunity to discover novel and exciting transformations that go far beyond what currently possible. Achieving this project will provide unprecedented tools for the preparation and the use of borylated materials in synthesis and catalysis.