Diversification of aliphatic C–H bonds in small molecules and polyolefins via radical chain transfer

The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and polymers. Herein, we report an approach to aliphatic C–H diversification via radical chain transfer featuring an easily prepared O- alkenylhydroxamate reagent, which upon mild heating facilitates a range of challenging or previously undeveloped aliphatic C–H functionalizations of small molecules and polyolefins. This broad reaction platform enabled the functionalization of post-consumer polyolefins in infrastructure used to process plastic waste. Furthermore, the chemoselective placement of ionic functionality onto a branched polyolefin via C–H functionalization upcycled the material from a thermoplastic into a tough elastomer with the tensile properties of high-value polyolefin ionomers. A simple reagent enables the broad diversification of unactivated, aliphatic C–H bonds in small molecules and post-consumer plastic waste.