Fluorine-containing organic molecules have become an indispensable in medicinal chemistry, agrochemistry, materials science, and biology.Despite all these applications in many fields of chemistry, there are limited ways to access most fluorinated molecules, especially organic molecules containing aliphatic fluorides.Ideally, one would like to access aliphatic fluorides through direct functionalization of sp3 C–H bonds (via radical based routes), and this would open limitless possibilities to synthesize a variety of fluorinated molecules.Recently, our laboratory and others accomplished a notable improvement in controlling the reactivity of aliphatic C–H bonds towards radical based fluorinations, but had only demonstrated selective sp3 C–H bond fluorination on highly symmetric substrates or those containing more activated benzylic C–H bonds.As a next step in progress, there was a great need to direct radical fluorination in complex natural products.We envisioned two approaches to accomplish this task through directed sp3 C–C bond cleavage or C–H bond functionalization.Accordingly, herein, directed-fluorination methods, and advances in selectivity in functionalizing peptides, terpenoids, and other complex organic molecules using either guided C–C cleavage or carbonyl groups to target unactivated C–H bondsare discussed.These strategies have helped radical based fluorination reactions become a valuable synthetic approach to functionalize complex natural products through late-stage fluorination.Additionally, we briefly explored the use of cyclopropanol derived radicals to couple with electron deficient heteroaromatic rings.
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DIRECTED sp3 C–C AND C–H BOND CLEAVAGE FOR RADICAL BASED FUNCTIONALIZATIONS
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