Radical Cascade Combining Cross-Olefin Coupling with the Smiles-Truce Rearrangement

Radical cascade reactions enable the swift and efficient assembly of complex molecular architectures. These transformations are especially valuable when initiated from readily available substrates bearing native functionalities. In this work, we describe the development of a cascade reaction that selectively combines two alkene starting materials, forming three new bonds in a single step. This transformation is initiated by polarity-matched, catalytic hydrogen atom transfer from a cobalt catalyst to an electron-rich styrene double bond. Subsequent Giese-addition of the carbon-centred radical occurs and, when using N-sulfonyl acrylamides as the Michael acceptors, a radical cascade reaction is triggered to yield α,γ-diarylated amides via Smiles-Truce rearrangement. This allows for the construction of complex organic molecules with sterically hindered aryl substituents in a swift manner under mild conditions.