Photoinduced Fluoroalkylalkynylation of Unactivated Alkenes with Terminal Alkynes

Herein, we report a photoinduced fluoroalkylalkynylation of alkenes with terminal alkynes under mild conditions, without the need for coupling metal catalysts or preformed alkynyl reagents. It proceeds via a radical cascade that hinges on regenerating a key intermediate from the ATRA adduct through two paths: photocatalyst-mediated SET and phosphine-mediated XAT. Consequently, it offers a straightforward and atom-economical route to valuable β-fluoroalkyl alkynes.