A visible-light-initiated
trifluoromethylation/remote aliphatic
C–H alkynylation of α-alkyl-substituted vinyl azides
using acetylenic triflones as both the trifluoromethyl and alkyne
donors is described. The reaction occurred under environmentally benign
and radical initiator-free reaction conditions, affording γ-alkynylated
trifluoromethyl ketone derivatives with a broad scope of substituents.
Mechanistic studies suggested that the reaction is initiated via a triplet–triplet energy transfer between the
4CzIPN catalyst and acetylenic triflone, followed by fragmentation
to generate a trifluoromethyl radical and an alkynyl radical.