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. 2024 Apr 8;17(7):e202301472.
doi: 10.1002/cssc.202301472. Epub 2023 Dec 8.

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

Nicolas Joly  1   2 , Alessandro Colella  1 , Monique-Edwige Mendy  1   3 , Mbaye Diagne Mbaye  3 , Sylvain Gaillard  1 , Albert Poater  2 , Jean-Luc Renaud  1   4
Affiliations

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

Nicolas Joly et al. ChemSusChem. .

Abstract

A visible-light-induced iron-catalyzed α-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. γ,δ-Unsaturated ketones can now be accessed through this borrowing hydrogen methodology at room temperature. Mechanistic investigations revealed that the steric hindrance on the δ-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.

Keywords: hydrogen auto-transfer; iron complex; light activation; γ,δ-unsaturated ketones.

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