Visible-Light-Mediated Two-Fold Unsymmetrical C(sp3)−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 sp3 C−H functionalization of tertiary amines with the formation of two different C−C bonds (one sp3-sp3 bond, one sp2-sp3 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. [ABSTRACT FROM AUTHOR]