Scissoring Enaminone C=C Double Bond by Free Radical Process for the Synthesis of α-Trifluoromethyl Ketones with CF3SO2Na

The C=C double bond cleavage on tertiary enaminones, enabling the formation of a new C-CF3 bond, has been realized as a practical method for the synthesis of alpha-trifluoromethyl ketones with only the promotion of TBHP and ambient heating. Control experiments support that the reactions proceed via a featured free radical process. The deuterium labeling experiment employing D2O indicates that water participated in the product formation by donating the hydrogen atom for the newly generated alpha-C-H bond in the product.

Automated summary

A new method for the synthesis of α-trifluoromethyl ketones has been developed by cleaving the C=C double bond on tertiary enaminones to form a new C-CF3 bond, with the promotion of TBHP and ambient heating. Control experiments show that the reactions proceed via a featured free radical process, and deuterium labeling experiments indicate the involvement of water in product formation by providing hydrogen atoms.