Diversification of aliphatic C–H bonds in small molecules and polyolefins through 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 carbon–hydrogen bond diversification using radical chain transfer featuring an easily preparedO -alkenylhydroxamate reagent, which upon mild heating facilitates a range of challenging or previously undeveloped aliphatic carbon–hydrogen bond functionalizations of small molecules and polyolefins. This broad reaction platform enabled the functionalization of postconsumer polyolefins in infrastructure used to process plastic waste. Furthermore, the chemoselective placement of ionic functionality onto a branched polyolefin using carbon–hydrogen bond functionalization upcycled the material from a thermoplastic into a tough elastomer with the tensile properties of high-value polyolefin ionomers.