Visible Light-Enabled Oxo-Alkylation of Styrenes with Aliphatic Alcohol Derivatives for the Synthesis of α-Alkyl Ketones.

Herein, we report a visible-light-enabled oxo-alkylation of styrenes utilizing aliphatic alcohol-derived N-alkoxyphthalimides (NAPIs) as alkyl radical precursors. Distinct from conventional deoxygenative approaches that retain the parent scaffold, this protocol proceeds via a deconstructive mechanism involving the β-fragmentation of alkoxy radicals. This strategy enables the synthesis of diverse α-alkyl ketones from a wide range of substrates, including primary, secondary, and tertiary alcohols, as well as various styrenes. Notably, the method facilitates the late-stage modification of complex natural scaffolds, such as sclareolide and β-pinene. Furthermore, the synthetic utility of this protocol is demonstrated through the one-carbon homologation of aliphatic alcohols.