DOI: 10.1002/anie.202317770 ISSN: 1433-7851

Catalyst‐free Trifluoromethoxylation of Silyl Enol Ethers and Allyl Silanes with Bis(trifluoromethyl)peroxide

Lilian Maria Maas, Carlo Fasting, Patrick Voßnacker, Niklas Limberg, Paul Golz, Carsten Müller, Sebastian Riedel, Matthew Neil Hopkinson
  • General Chemistry
  • Catalysis

Radical trifluoromethoxylation is an attractive approach to prepare compounds featuring the important OCF3 group, however most existing methods have focused on aromatic substrates. Here, we report novel methodologies with alkenyl substrates employing bis(trifluoromethyl)peroxide (BTMP) as a practical and comparatively atom economical trifluoromethoxylating reagent. With silyl enol ether substrates, switching reaction solvent allows for the synthesis of either α‐(trifluoromethoxy)ketone products or unprecedented alkenyl‐OCF3 species. Furthermore, allyl silanes have been employed as substrates for the first time, affording allyl(trifluoromethyl)ether products in good yields. In each case, the methods operate at room temperature without large excesses of the alkene substrate while, in contrast to previous radical trifluoromethoxylation reactions, no catalyst, light or other activators are required.

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