Photoinduced radical addition process enables deoxygenative hydroacylation and hydrophosphonylation of carbonyls

The homologation of carbonyls is an efficient and important pathway for the synthesis of ketone compounds; however, traditional methods often suffer from narrow scopes or harsh conditions. Although some useful improvements have been made to the original approach, these innovations, based on the identical two-electron mechanism, make it challenging to break through the intrinsic limitations. To address these inherent issues, herein, we develop a photoinduced deoxygenative hydroacylation of carbonyls via a single-electron process. The addition of acyl radicals that can be easily obtained via the hydrogen-atom-transfer process (to N-tosylhydrazones) as radical receptors instead of diazo precursors, followed by simple removal of the hydrazine group, enables a broad scope under mild conditions to achieve the transformation. This unique mode enables us to further extend the product range to amides. Additionally, the deoxygenative hydrophosphonylation of aldehydes for the rapid synthesis of phosphorus compounds can be obtained smoothly with this strategy.