Blue-Light Induced Iron-Catalyzed Synthesis of γ,δ-Unsaturated Ketones

A visible-light-induced iron-catalyzed alpha-alkylation of ketones with allylic and propargylic alcohols as pro-electrophiles is reported. The diaminocyclopentadienone iron tricarbonyl complex plays a dual role by harvesting light and facilitating dehydrogenation and reduction steps without the help of any exogenous photosensitizer. gamma,delta-Unsaturated ketones can now be accessed through this borrowing hydrogen methodology at room temperature. Mechanistic investigations revealed that the steric hindrance on the delta-position of either the dienone or ene-ynone intermediate is the key feature to prevent or decrease the competitive 1,6-reduction (and consequently the formation of the saturated ketone) and to favor the synthesis of a set of non-conjugated enones and ynones.