Photochemical Allylation of Aldehydes or Alkanes with Vinyl Cyclopropanes

Vinyl cyclopropanes are useful linchpins for the synthesis of more complex scaffolds. In this work, we present an acylation or alkylation protocol of donor–acceptor vinyl cyclopropanes, employing tetra‐n‐butylammonium decatungstate as the photocatalyst. In this novel photochemical protocol, the formation of allyl ketones or alkenes from vinyl cyclopropanes and aldehydes or alkanes is presented. A diverse range of substrates are compatible with this protocol as a plethora of aldehydes, aliphatic or aromatic, alkanes, and vinyl cyclopropanes, decorated with amides, esters, or other substituents, can be employed. The method was proven compatible and can be performed under flow conditions, while further manipulation of the desired products was also demonstrated. Mechanistic studies are also described, which complement the proposed mechanism.