Visible-Light-Mediated Two-Fold Unsymmetrical C(sp )-H Functionalization and Double C-F Substitution.

A visible-light-mediated [3+3] annulation of tertiary amines with α-trifluoromethyl alkenes was developed. The reaction offers a direct route to fluorinated tetrahydropyridines and azabicyclo[3.m.1] frameworks under very mild conditions. This protocol presents a rare example of dual sp C-H functionalization of tertiary amines with the formation of two different C-C bonds (one sp -sp bond, one sp -sp bond). Moreover, two consecutive C-F substitutions in a trifluoromethyl group were achieved in one pot using visible light photoredox catalysis, which enables an unprecedented ring construction.