Visible‐Light‐Mediated Two‐Fold Unsymmetrical C(sp3)−H Functionalization and Double C−F Substitution

Abstract 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 3 C−H functionalization of tertiary amines with the formation of two different C−C bonds (one sp 3 –sp 3 bond, one sp 2 –sp 3 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.