A photoredox approach to generate distal cyano-substituted alkyl radicals through C-C bond cleavage of cyclobutanone oximes was developed. The radicals produced by this method were applied to three-component cyanopropylation/etherification of unactivated alkenes. Their reactions with diverse radical acceptors were also demonstrated.

A photocatalytic decarboxylative/defluorinative [4 + 3] annulation of o-hydroxyphenylacetic acids and trifluoromethyl alkenes was developed. The reaction led to fluorinated dihydrobenzoxepines through two consecutive C–F substitutions in a CF3 group.

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.

An efficient method for the construction of fluorinated benzo[a]quinolizidines from a-trifluoromethyl alkenes and dihydroisoquinoline acetic acids using visible light photocatalysis was developed. The reaction was accomplished through a decarboxylative/defluorinative cross-coupling, followed by an intramolecular defluorinative CÀH functionalization in one-pot. Diversified fluorinated benzo[a]quinolizidines, which are less accessible by other methods, were obtained in good yields with high diastereoselectivity.

A radical defluorinative alkylation method of 1‐trifluoromethyl alkenes and 1,3‐butadienes with 4‐alkyl‐1,4‐dihydropyridines under visible light irradiation is presented. Various alkylated 1,1‐difluoroalkenes and 1,1‐difluorodienes were obtained in moderate to high yields through a sequential C−C and C−F bond cleavage process.