Radical trifluoromethylation of Ti ate enolate: possible intervention of transformation of Ti(IV) to Ti(III) for radical termination

The radical trifluoromethylation of ketone Ti ate enolates gave α-CF3 ketones in good yields. The use of excess amount of LDA and Ti(OiPr)4 in the preparation of Ti ate enolates is the key to the efficient radical trifluoromethylation. Theoretical studies on the spin density of the Ti(IV) ate ketyl radical intermediate suggest the involvement of transformation from Ti(IV) ate ketyl radical intermediates to Ti(III) species in a radical termination step.