Photochemical Alkylamination of Olefins through Reactivity-Based Sorting of Alkyl Radicals.

Alkyl radicals represent some of the most intriguing prospects in organic synthesis, showing diverse patterns of reactivity for versatile transformations. In light of this, the methyl radical, in addition to being a methylating agent, is also a good proposition for hydrogen atom transfer (HAT). Similarly, acetonitrile also has dual facets to its reactivity, acting as an amination reagent in the Ritter reaction while also being the progenitor to cyanomethyl radicals through HAT. We hereby take advantage of the merging of the dual reactivities of these radicals, allowing facile access to amines of various types from olefins when conjugated with a photoredox Ritter amination.